POLAR LIQUIDS WITH HIGH POROSITY AND USES THEREOF

Abstract

To increase the gas solubility of polar liquids, the invention leverages coordination chemistry, nanoscience, and porous materials design to create porous liquids, e.g., aqueous solutions, containing a high density of networks of dry pores—which will feature dramatically higher capacities for dissolved gases than conventional polar liquids.

Claims

1. A liquid composition comprising: a) a polar liquid; and b) a dispersion of porous particles, the pores of which comprise an internal surface that resists wetting by the polar liquid and an external surface that is wettable by the polar liquid, wherein the pores are sized to allow entry of a gas and molecules of the polar liquid.

2. The liquid composition of claim 1, wherein the internal surface is hydrophobic.

3. The liquid composition of claim 1, wherein the porous particles comprise a zeolite or metal-organic framework (MOF).

4. The liquid composition of claim 3, wherein the zeolite comprises silicalite-1, ZSM-5, or zeolite LTL or wherein the MOF comprises ZIF-8 or ZIF-67.

5. The liquid composition of any one of claims 1-4, wherein the particles are nanoparticles or microparticles.

6. The liquid composition of claim 5, wherein the particles are crystalline.

7. The liquid composition of claim 1, wherein the particles comprise a hydrophilic coating.

8. The liquid composition of claim 1, wherein the particles comprise a globular protein on the exterior.

9. The liquid composition of claim 8, wherein the globular protein is BSA, HSA, ovalbumin, or lactalbumin.

10. The liquid composition of claim 1, wherein the particles comprise a covalently or non-covalently attached hydrophilic organic polymer coating.

11. The liquid composition of claim 10, wherein the hydrophilic organic polymer coating is covalently attached to the particles by β-hydroxyalkyl covalent linkages.

12. The liquid composition of claim 1, further comprising the gas dissolved in the composition and located in the pores of the porous particles.

13. The liquid composition of claim 1, wherein the pores resist ingress of the polar liquid below an applied pressure of 100 bar at room temperature.

14. The liquid composition of claim 1, wherein the pores resist ingress of the polar liquid below an applied pressure of 200 bar at room temperature.

15. The liquid composition of claim 1, wherein the pores resist ingress of the polar liquid below an applied pressure of 900 bar at room temperature.

16. A composition comprising a plurality of microporous nanoparticles, the pores of which comprise an internal surface that resists wetting by a polar liquid and an external surface that is wettable by the polar liquid, wherein the pores are sized to allow entry of a gas and molecules of the polar liquid.

17. The composition of claim 16, wherein the porous particles comprise a zeolite or metal-organic framework.

18. The composition of claim 17, wherein the zeolite comprises silicalite-1 or ZSM-5 or zeolite LTL; or wherein the MOF comprises ZIF-8 or ZIF-67.

19. The composition of any one of claims 16-18, wherein the particles are nanoparticles or microparticles.

20. The composition of claim 19, wherein the particles are crystalline.

21. The composition of claim 16, wherein the particles comprise a hydrophilic coating.

22. The composition of claim 16, wherein the particles comprise a globular protein on the exterior.

23. The composition of claim 22, wherein the globular protein is BSA, HSA, ovalbumin, or lactalbumin.

24. The composition of claim 16, wherein the particles comprise a covalently or non-covalently attached hydrophilic organic polymer coating.

25. The composition of claim 7 wherein the hydrophilic organic polymer coating is covalently attached to the particles by β-hydroxyalkyl covalent linkages.

26. A method of storing a gas in a polar liquid, comprising: providing a dispersion of porous particles in the polar liquid, wherein the pores of the particles comprise an internal surface that resists wetting by the polar liquid and an external surface that is wettable by the polar liquid, wherein the pores are sized to allow entry of the gas and molecules of the polar liquid; and dissolving the gas in the dispersion, wherein the gas is stored in the pores.

27. The method of claim 26, wherein the internal surface is hydrophobic.

28. The method of claim 26, wherein the gas comprises argon, oxygen, nitrogen, carbon dioxide, carbon monoxide, xenon, methane, helium, neon, or hydrogen.

29. The method of claim 26, wherein the porous particles disintegrate after dissolution of the gas in the dispersion.

30. The method of any one of claims 26-29, wherein the porous particles are porous particles according to any one of claims 16-25.

31. A method of introducing a gas into a biological system, comprising: providing a dispersion of porous particles in a polar liquid, wherein the pores of the particles comprise an internal surface that resists wetting by the polar liquid and an external surface that is wettable by the polar liquid, wherein the pores are sized to allow entry of the gas and molecules of polar the liquid; wherein the gas is stored in the pores; and contacting the dispersion with the biological system.

32. The method of claim 31, wherein the porous particles are porous particles according to any one of claims 16-25.

33. A method of increasing the volumetric mass transfer of a gas to a substrate comprising: providing a dispersion of porous particles in a polar liquid, wherein the pores of the particles comprise an internal surface that resists wetting by the polar liquid and an external surface that is wettable by the polar liquid, wherein the pores are sized to allow entry of the gas and molecules of the polar liquid; wherein the gas is stored in the pores; and contacting the dispersion with the substrate and allowing the gas to react therewith.

34. The method of claim 33, wherein the porous particles are porous particles according to any one of claims 16-25.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG. 1. Structure and chemical composition of metal organic framework (MOF) nanoparticles utilized in certain embodiments of the invention. The illustrated zeolitic imidazolate frameworks (ZIFs) have high pore volumes and hydrophobicity. ZIF-8 has zinc metal nodes coordinated by 2-methylimidazole linkers, while ZIF-67 has cobalt metal nodes with identical organic linkers.

[0019] FIGS. 2a-2b. A schematic depicting two different covalent functionalization approaches for ZIF nanoparticles (a) and the initial target ligands (b). Carbene derivatives and diazonium mediated PEG-grafting are reported to bond strongly on open metal sites without altering the original organic linker, while the imidazole-based Schiff bases proceed by linker exchange.

[0020] FIGS. 3a-3b. Results for surface functionalization of ZIF-8 via diazonium mediated PEG grafting (a) and that of ZIF-67 with imidazole-based Schiff base formation (b). ZIF-8 functionalization showed prolonged stability and dispersibility. On the other hand, the ZIF-67 sample showed dispersibility but was slowly hydrolyzed due to its open metal sites over the course of a few days. The preliminary results show that one can achieve controlled release of adsorbed gas over a desired time period through modulating the functionalization ligand.

[0021] FIGS. 4a-4g. Creating aqueous fluids with permanent porosity. (a) Illustration of the thermodynamic approach to designing porous water, whereby porous nanocrystals with hydrophobic internal surfaces and hydrophilic external surfaces form stable, uniform dispersions in water that contain permanently dry pores capable of adsorbing gas molecules. (b) The O.sub.2 and CO.sub.2 sorption capacities of two hydrophobic zeolitic imidazolate frameworks (ZIF-8 and ZIF-67) and one hydrophobic zeolite (silicalite-1) are compared to those of pure H.sub.2O, a representative perfluorocarbon solvent (C.sub.7F.sub.16), and the density of the bulk gas phase. All O.sub.2 and CO.sub.2 densities are at 1 bar and 25° C. and include the volume occupied by the solid adsorbent or liquid solvent. (c) Crystal structure of silicalite-1 highlighting its external surface that is terminated by surface silanol groups and is intrinsically hydrophilic. Vertices of tetrahedra and spheres represent Si and O atoms, respectively. (d) Crystal structure of ZIF-8 and an illustration of strategies to increase the hydrophilicity of its external surface through covalent functionalization via reaction with hydrophilic epoxides and non-covalent functionalization via the adsorption of the protein bovine serum albumin (BSA). Dark yellow tetrahedra, grey spheres, and blue spheres represent Zn, C, and N atoms, respectively; H atoms are omitted for clarity. (e-g) Dynamic light scattering (DLS) particle size distributions for diluted aqueous solutions of (e) silicalite-1, (f) (mPEG)ZIF-8, and (g) BSA/ZIF-67. The insets show photos of solutions at nanocrystal concentrations of 12 vol %, 4 vol %, and 3 vol %, respectively.

[0022] FIGS. 5a-5b. Density measurements to evaluate the porosity of aqueous solutions. The density of a porous solution with dry pores will be lower than the density of an analogous nonporous solution with solvent-filled pores. The measured densities (circles) of several porous nanocrystal dispersions are plotted as a function of nanocrystal concentration at 25° C. Theoretical densities as a function of nanocrystal concentration are indicated by shading, with grey corresponding to a solution with completely dry pores and blue or purple corresponding to a solution with pores filled with aqueous solution or ethanol (EtOH), respectively, at the same density as the bulk solvent. (a) The densities of dispersions of silicalite-1, BSA/ZIF-67, and (mPEG)ZIF-8 nanocrystals in water are consistent with porous solutions containing dry pores. (b) In contrast, the densities of dispersions of silicalite-1 nanocrystals in EtOH and zeolite LTL (Linde Type L) and PEG/ZIF-8 nanocrystals in water are consistent with solutions that have no accessible porosity. Note that the density of nanoconfined solvent is often lower than the bulk solvent density.

[0023] FIGS. 6a-6c Equilibrium gas absorption isotherms of aqueous solutions. Gas absorption isotherms for (a) O.sub.2 and (b) CO.sub.2 in a 12 vol % solution of silicalite-1 nanocrystals in water and a 5.1 vol % of zeolite LTL in water at 25° C. Lines represent linear fits to the isotherm data, with the exception of a single-site Langmuir fit for CO.sub.2 absorption in the silicalite-1 solution. The O.sub.2 and CO.sub.2 solubilities of pure water at 25° C. are indicated with lines. (c) The amount of O.sub.2 and CO.sub.2 absorbed by the zeolite nanocrystals in aqueous solution relative to the zeolite solid-state gas capacities (see FIGS. 11a, 11b, 23a, 23b, and Table 6), which is obtained by accounting for the pure water gas solubility. Error bars represent the standard deviations associated with pure water control experiments (Table 9).

[0024] FIGS. 7a-7d. (a) O.sub.2 release kinetics for injections of oxygenated silicalite-1, (mPEG)ZIF-8, and BSA/ZIF-67 nanocrystal solutions into deoxygenated water. All solutions were injected into a 1.2-mL gas-tight vial, and the injection volumes are indicated next to the arrows. (b) The amount of O.sub.2 delivered by oxygenated aqueous solutions of hydrophobic zeolite and MOF nanocrystals relative to the theoretical amount calculated by assuming fully dry pores with gas capacities equivalent to those measured in the solid state. (c) Comparison of the O.sub.2 carrying capacities of aqueous solutions of hydrophobic zeolite and MOF nanocrystals to the O.sub.2 carrying capacities of blood (15 g Hb/dL) and two representative perfluorocarbon emulsions (Fluosol and Oxygent). All capacities are for solutions equilibrated at 1 bar O.sub.2 near ambient temperature. (d) The amount of O.sub.2 delivered to deoxygenated packed red blood cells (RBCs) by oxygenated solutions of (mPEG)ZIF-8 (6.7 vol %) and silicalite-1 nanocrystals (9.1 vol % and 10.8 vol % for 60 and 90 nm nanocrystals, respectively) as a function of the volume of solution injected. The O.sub.2 capacities of each solution are calculated from the slope of linear fits to the data. Note that all solutions were equilibrated at 1 bar O.sub.2 at ambient temperature and contain 5% dextrose. Inset: representative O.sub.2 release kinetics for a single injection of 100 pL solution of 60-nm silicalite-1 nanocrystals. The arrow indicates the approximate timepoint of the injection.

[0025] FIGS. 8a-8u Density measurements. Solution density (black circles) as a function of concentration and temperature for (a-c) colloidal solutions of 90-nm silicalite-1 nanocrystals in water, (d-f) a colloidal solution of silicalite-1 nanocrystals with 5 wt % dextrose in water, (g-i) colloidal solutions of 90-nm silicalite-1 nanocrystals in ethanol, (j-l) colloidal solutions of zeolite LTL nanocrystals in water, (m-o) colloidal solutions of (mPEG)ZIF-8 nanocrystals in water, (p-r) a colloidal solution of (mPEG)ZIF-8 with 5 wt % dextrose in water, and (s-u) colloidal solutions of ZSM-5 nanocrystals (Si/Al=64) in water. A gradient shows the possible range of theoretical densities for different degrees of pore filling, from air-filled to solvent-filled pores. Note that the maximum pore filling density corresponds to the bulk solvent density, but the density of nanoconfined solvent is often lower than the bulk solvent density.

[0026] FIG. 9 Viscosity measurements. The viscosity of colloidal solutions of 90-nm silicalite-1 nanocrystals in water at 25° C. as a function of concentration.

[0027] FIGS. 10a-10c Surface area and pore volume measurements. (a) 77 K N.sub.2 adsorption (closed circles) and desorption (open circles) isotherms for ZIF-67, ZIF-8, zeolite LTL, and silicalite-1 before functionalization (if applicable) and dispersion in water. Calculated BET surface areas and pore volumes are listed in Table 4.

[0028] (b) 77 K N.sub.2 adsorption isotherms for 60-nm silicalite-1 and ZSM-5 nanocrystals before dispersion in water. The pore volume of 60-nm silicalite-1 calculated by the t-plot method (fit range 3.5 to 9.8 Å) is 0.16 mL/g, which is consistent with the pore volume of 90-nm silicalite-1 (FIG. 16). The pore volume calculated by the t-plot method (fit range (4.7 to 13 Å) of ZSM-5 is 0.17 mL/g, which is also consistent with silicalite-1 nanocrystals. (c) 77 K N.sub.2 adsorption (closed circles) and desorption (open circles) isotherms for ZIF-8 nanocrystals before and after functionalization with mPEG, showing that covalent functionalization has minimal impact on the accessible surface area.

[0029] FIGS. 11a-11d Solid-state isotherms. O.sub.2 adsorption isotherms at (a, b) 25° C. and (c, d) 37° C. in the solid state are plotted on a gravimetric and volumetric basis. Volumetric values are calculated from gravimetric values using the crystallographic density. Consistent with the accessible surface area, covalent functionalization of ZIF-8 has a negligible impact on adsorption of O.sub.2 as demonstrated by comparing the adsorption for ZIF-8 and (mPEG)ZIF-8.

[0030] FIGS. 12a-12g External surface area in the solid state. Analysis of external surface area by the t-plot method using the Harkins and Jura thickness curve for (a) 90-nm silicalite-1 nanocrystals, (b) ZIF-8 nanocrystals, (c) (mPEG)ZIF-8, and (d) ZIF-67. Solid-state adsorption isotherms for 90 nm silicalite-1 nanocrystals before and after calcination, demonstrating the lack of accessible porosity in non-calcined samples and the contribution of external surface area to adsorption in calcined silicalite-1. (e) t-plot analysis indicating that the total surface area of non-calcined silicalite-1 is consistent with the external surface area of calcined silicalite-1 (Table 4). Adsorption isotherms for (f) O.sub.2 and (g) CO.sub.2 are compared for calcined and non-calcined silicalite-1 nanocrystals at 25° C.

[0031] FIG. 13 Cycling data. O.sub.2 capacity of a 9.7 vol % colloidal solution of 90-nm silicalite-1 nanocrystals at 0.2 bar and 15° C. over 3 sorption-desorption cycles. One cycle consists of dosing O.sub.2 to the solution, waiting for equilibration, and then degassing the solution.

[0032] FIGS. 14a-14c Absorption equilibration. Raw pressure vs. time data (black circles) for volumetric O.sub.2 absorption experiments at 25° C. in a colloidal solution of 90-nm silicalite-1 nanocrystals in water (12.0 vol%). Three successive doses to the sample without intermediate degassing are shown in order of occurrence from (a) to (c). For each plot, the red line corresponds to a pseudo-first order fit (Eqn 4), and the fitted equilibrium pressure is indicated with a dashed black line.

[0033] FIGS. 15a-15e Colloidal stability. DLS measurements of colloidal solutions of (a) silicalite-1 nanocrystals, (b) (mPEG)ZIF-8 nanocrystals, and (c) ZSM-5 nanocrystals at ambient temperature are shown directly after the nanocrystals were dispersed (t=0) and after waiting for the specified amount of time. For silicalite-1 and ZSM-5, the starting dispersions were at concentrations of 12 and 37 vol %, respectively, and were then diluted 100-fold and 250-fold, respectively. Dilution was required to get accurate particle size distributions for high-concentration samples. For (mPEG)ZIF-8, the starting solution was at a concentration of 7 wt %, which was diluted to 2 wt % immediately prior to measurement. Inset images are of aqueous dispersions of (a) 90-nm silicalite-1 (12 vol %) after 2 months, (b) (mPEG)ZIF-8 (4 vol %) after 7 weeks, and (c) high-concentration ZSM-5 nanocrystals (39 vol %) after 1 week. (d, e) Images of pure ZIF-67 (4.0 vol%), PEG/ZIF-67 (3.6 vol% ZIF-67), and PEG/ZIF-67 (3.6 wt % ZIF67) (d) immediately after dispersing in water and (e) after 7 days. As evidenced by the color change to dark red, pure ZIF-67 is prone to hydrolytic degradation, but degradation is inhibited by noncovalent functionalization with BSA or PEG.

[0034] FIGS. 16a-16h SEM Images. Representative scanning electron microscopy (SEM) images of nanocrystals used to form colloidal solutions in water: (a) silicalite-1 (average diameter=59±8 nm), (b) silicalite-1 (average diameter=90±16 nm), (c) zeolite LTL, (d) ZSM-5 (average diameter=238±23 nm), (e) as-synthesized ZIF-8 nanocrystals (average diameter=103±10 nm), (f) (mPEG)ZIF-8 nanocrystals that had been dispersed in water for one week (average diameter=98±7 nm), (g) BSA/ZIF-67 (average diameter=844±103 nm) and (h) PEG/ZIF-67 aqueous solutions (average diameter=941±147 nm).

[0035] FIG. 17 Summary of O.sub.2 carrying capacities. Amount of O.sub.2 stored in nanocrystal solutions determined by measurement of the amount of O.sub.2 released upon injection of an oxygenated solution into deoxygenated water, along with the percentage of the experimental amount of O.sub.2 released relative to the theoretical amount for a porous solution based on solid-state O.sub.2 adsorption data. At least three measurements were made for each material to obtain an average value and standard deviation. Note that all solutions were equilibrated with 1 bar of O.sub.2 at ambient temperature, except for PEG/ZIF-8 and PEG/ZIF-67 which were equilibrated with air (0.2 bar O.sub.2).

[0036] FIGS. 18a-18f Ambient temperature powder X-ray diffraction patterns of dried aqueous solutions of (a) silicalite-1 (90-nm nanocrystals, 12.0 vol %), (b) silicalite-1 (60-nm nanocrystals, 10.0 vol %), (c) zeolite LTL (9.0 vol %), (d) PEG/ZIF-67 (3.4 vol %), (e) BSA/ZIF-67 (3.4 vol %), and (f) (mPEG)ZIF-8 (7 vol %). In each panel, the bottom curve represents the calculated diffraction pattern while the top curve represents the experimental diffraction pattern.

[0037] FIG. 19 Ambient temperature powder X-ray diffraction pattern of a dried aqueous solution of ZSM-5 nanocrystals (37.5 vol %). The bottom curve represents the calculated diffraction pattern while the top curve represents the experimental diffraction pattern.

[0038] FIGS. 20a-20b (a) O.sub.2 and (b) CO.sub.2 adsorption at 25° C. for 90-nm and 60-nm silicalite-1 nanocrystals, indicating that particle size has a negligible effect on adsorption capacity.

[0039] FIGS. 21a-21b Solid-state O.sub.2 adsorption isotherms at 15° C. on a (a) gravimetric (mmol O.sub.2/g solid) and (b) volumetric (mmol O.sub.2/L solid) basis. Volumetric values are calculated from gravimetric values using the crystallographic density of the solid.

[0040] FIGS. 22a-22b Solid-state N.sub.2 adsorption isotherms at 25° C. on a (a) gravimetric (mmol N.sub.2/g solid) and (b) volumetric (mmol N.sub.2/L solid) basis. Volumetric values are calculated from gravimetric values using the crystallographic density of the solid.

[0041] FIGS. 23a-23b Solid-state CO.sub.2 adsorption isotherms at 25° C. on a (a) gravimetric (mmol CO.sub.2/g solid) and (b) volumetric (mmol CO.sub.2/L solid) basis. Volumetric values are calculated from gravimetric values using the crystallographic density of the solid.

[0042] FIGS. 24a-24c Solid-state adsorption isotherms for ZIF-8 nanocrystals before and after functionalization with mPEG, showing that covalent functionalization has a negligible impact on the adsorption of O.sub.2 and N.sub.2 near ambient temperature. Isotherms are shown for (a) O.sub.2 at 15° C., (b) O.sub.2 at 37° C., (c) N.sub.2 at 25° C. Volumetric values are calculated from gravimetric values using the crystallographic density of ZIF-8, since external surface functionalization with mPEG is assumed to have a negligible effect on the crystallographic density.

[0043] FIGS. 25a-25b DLS measurements of colloidal solutions of (a) PEG/ZIF-8 and (b) PEG/ZIF-67 in water. The starting solutions contained 30 wt % PEG and 20 wt % ZIF-8 or 7 wt % ZIF-67. Each sample was diluted 100-fold immediately prior to measurement in order to obtain accurate DLS data.

[0044] FIG. 26 .sup.1H-NMR (400 MHz, DMSO-d.sub.6) of mPEG/ZIF-8 nanocrystals digested with a 35 wt % DCI solution in D.sub.2O. δ=7.67 (d, 2H), 3.55-3.35 (m), 3.23 (s, 3H) for mPEG-mIm, and δ=7.52 (s, 2H), 2.56 (s, 3H) for mIm. Note that some mPEG protons could not be accurately quantified due to signal overlap with solvent and low signal-to-noise ratio.

[0045] FIG. 27 ESI-MS spectrum of mPEG/ZIF-8 nanocrystals after digestion with 1M HCl that was added to be approximately 1 wt % of the sample solution. Mass calculated for [M+nH].sup.+ (bottom) and mass found (top).

DETAILED DESCRIPTION OF THE INVENTION

[0046] The invention provides compositions and methods for storing gases in liquids. Liquids (e.g., water) with permanent porosity can store, transport, and deliver high densities of gas molecules within liquid, e.g., aqueous, environments.

[0047] Since dissolving a gas inside a liquid requires overcoming an energy barrier associated with the creation of sufficient space—or porosity—to accommodate the incoming gas molecules, liquids with intrinsic porosity can, in principle, alter the fundamental thermodynamics of gas absorption within a liquid. Specifically, empty pores may substantially reduce—or even eliminate—enthalpic and entropic penalties for solvent rearrangement during gas absorption while simultaneously generating new attractive interactions (FIG. 4a). Embodiments of the invention use the combined effect to achieve a dramatic increase in the density of gas molecules present within solutions, with gas solubility increasing as the density of empty pores increases.

[0048] The invention is based on the discovery that liquids with permanent porosity (e.g., microporosity, e.g., including microporous particles) can absorb larger quantities of gas molecules than conventional solvents, providing new opportunities for liquid-phase gas storage, transport, and reactivity. Approaches to designing porous liquids which rely on sterically bulky solvent molecules or surface ligands, may not, however, be amenable to many important solvents, including water. The invention provides a generalizable thermodynamic strategy to create permanent porosity in liquid water. For example, the external and internal surface chemistry of porous materials such as porous zeolite and metal—organic framework nanocrystals can be tailored to promote the formation of stable dispersions in, e.g., water, while maintaining dry networks of internal pores that are accessible to gas molecules. As a result of their permanent porosity, these liquids (e.g., aqueous fluids) can concentrate gases, including oxygen (O.sub.2) and carbon dioxide (CO.sub.2), to much higher densities than are found in typical aqueous environments. When the liquids are oxygenated, this allows record-high capacities of O.sub.2, which can, e.g., be delivered to hypoxic red blood cells, highlighting the potential of this new class of porous liquids for physiological gas transport.

[0049] Water is the ubiquitous solvent for all biological processes and for many of the chemical transformations critical to sustainable energy generation, storage, and utilization. Its polarity and propensity for hydrogen bonding promote the solvation of polar substances but inhibit the dissolution of nonpolar ones, including most gases. The low solubility of gases in water—often an order of magnitude less than in common organic solvents—imposes fundamental limitations on many biomedical and energy-related technologies that require the transport of gas molecules through aqueous fluids. For instance, low densities of dissolved O.sub.2 hinder tissue engineering and cell culture in vitro and make it challenging to treat various types of life-threatening hypoxia in vivo. Aqueous-phase gas transport also limits the performance of fuel cells and the space-time yield and efficiency of many important electrocatalytic reactions—including CO.sub.2 reduction, N.sub.2 reduction, and CH.sub.4 oxidation.

Compositions

[0050] The invention employs porous particles that are dispersible in a liquid. The liquid wets the exterior of the particles but not the interior of the pores. The liquid may be a polar liquid, e.g., a polar protic solvent, e.g., water, an alcohol, such as methanol, ethanol, isopropanol, or propan-1-ol, or a mixture thereof. In certain embodiments, porous liquids rely on the synthesis of porous particles, e.g., porous nanocrystals with hydrophobic internal surfaces and hydrophilic external surfaces. The hydrophobic internal surfaces prevent polar liquids, e.g., H.sub.2O, from intruding into the porous networks of the nanocrystals by making it more thermodynamically favorable for H.sub.2O to remain in the bulk liquid phase. The hydrophilic external surfaces, which may be intrinsic to the porous material or created through the covalent attachment or non-covalent association of hydrophilic or amphiphilic surface ligands, allow the particles, e.g., nanocrystals, to be uniformly dispersed in polar liquids, such as H.sub.2O, to create a stable, homogeneous fluid. In addition to promoting dispersibility, surface ligands may also provide a kinetic barrier to liquid intrusion.

[0051] Owing to their high internal surface areas, variable pore diameters, and well-defined sites for external surface functionalization, two classes of highly tunable porous materials: zeolites and metal—organic frameworks may be employed in the invention. Particles may also include activated carbon or amorphous porous silica particles. Both zeolites and metal—organic frameworks feature internal networks of angstrom-sized pores that lead to high internal surface areas, often exceeding 1,000 m.sup.2 per g or mL of material. Porous particles of the invention may have average pore diameters of between about 3 Å and about 20 Å, e.g., between about 3-5 Å, 4-6 Å, 4-10 Å, 5-10 Å, 5-15 Å, 6-8 Å, 7-9 Å, 9-11 Å, 10-12 Å, 10-15 Å, 10-20 Å, 12-15 Å, 13-18 Å, 14-18 Å, 17-19 Å, 18-20 Å, or about 19-20 Å, e.g., about 5 Å, about 10 Å, about 15 Å, or about 20 Å. Even when surface interactions with gas molecules are relatively weak, these high internal surface areas concentrate gas molecules to densities that surpass those which are possible in a conventional liquid and in the bulk gas phase—even after accounting for the space occupied by the atoms framing the pore (FIG. 4b). By preventing liquid, e.g., water molecules, from entering these pores, the invention provides porous liquids and brings the high gas capacities of porous materials to solutions, e.g., aqueous. Porous particles of the invention may range in cross-sectional dimension (e.g., diameter) from about 5 nm to about 1000 nm, e.g., between about 5-100 nm (e.g., about 5-10 nm, 5-15 nm, 5-25 nm, 10-20 nm, 25-50 nm, 20-40 nm, 30-60 nm, 50-75 nm, 60-80 nm, 75-100 nm, 70-90 nm, 80-95 nm, or 90-100 nm) or about 100-1000 nm (e.g., about 100-150 nm, 120-160 nm, 140-180 nm, 150-200 nm, 100-200 nm, 100-300 nm, 200-500 nm, 250-750 nm, 300-400 nm, 350-650 nm, 400-500 nm, 400-600 nm, 500-750 nm, 600-800 nm, 750-1000 nm, 600-950 nm, 700-900 nm, 800-1000 nm, or 900-1000 nm). The porous particles may account for less than 0.1 vol % or up to 90 vol % of the composition, for example between about 0.01 vol % to about 90 vol %, e.g., about 0.01 to about 1 vol % (e.g., about 0.01-0.05 vol %, 0.02-0.07 vol %, 0.04-0.09 vol %, 0.05-0.1 vol %, 0.06-0.12 vol %, 0.1-0.15 vol %, 0.1-0.2 vol %, 0.1-0.5 vol %, 0.2-0.6 vol %, 0.3-0.7 vol %, 0.4-0.9 vol %, 0.5-0.9 vol %, 0.5-1 vol %, or 0.9-1 vol %) or, e.g., about 1 vol % to about 10 vol % (e.g., about 1-2 vol %, 1-3 vol %, 1-4 vol %, 2-5 vol %, 2-6 vol %, 3-7 vol %,4-8 vol %, 5-7 vol %, 5-10 vol %, 6-9 vol %, 7-10 vol %, 8-10, or 9-10 vol %), or about 10 vol % to about 90 vol (e.g., about 10-15 vol %, 10-20 vol %, 10-50 vol %, 15-45 vol %, 25-50 vol %, 30-60 vol %, 40-80 vol %, 50-75 vol %, 50-90 vol %, 60-90 vol %, 65-85 vol %, 70-85 vol %, 75-90 vol %, or 80-90 vol %). Representative scanning electron microscopy (SEM) images of nanocrystals according to embodiments of the invention used to form liquid suspensions, e.g., colloidal solutions in water, of the invention are shown in FIGS. 16a-6h. Ambient temperature powder X-ray diffraction patterns of some compositions of the invention (e.g., liquid suspension of microporous particles of the invention) are shown in FIGS. 18a-18f and 19.

[0052] Certain embodiments of the invention include the use of various MFI-type zeolite nanoparticles, both in pure silica form (known commonly as “silicalite-1”) and in Al-containing form (known as “ZSM-5”). The Si:Al ratios may be up to 50 or from 50 to infinity.

[0053] The high internal surface areas and pore volumes of porous particles (e.g., microporous particles), such as those of the invention, can concentrate gas molecules through adsorption to far higher densities than can be dissolved within a typical liquid solvent—or than exist in a bulk gas phase—at a given temperature and pressure. Porous liquids can include porous crystals (e.g., nanocrystals) or organic cage molecules dispersed in bulky organic solvents or ionic liquids that are too large to diffuse through the pore entrances, leaving the pores vacant and accessible to gas molecules. Because of their intrinsic porosity, these liquids can store much higher quantities of gas molecules than the corresponding nonporous liquid. This sterics-based approach to creating permanent porosity within liquids is not, however, transferable to aqueous systems because a pore that is large enough to adsorb nearly any gas molecule will also be large enough to accommodate H.sub.2O molecules. As a result, the high gas capacities of porous solids have yet to be exploited for aqueous-phase gas transport.

[0054] The invention includes liquids with permanent porosity and high gas sorption capacities based on thermodynamics rather than sterics (FIG. 4a). In some embodiments, porous particles (e.g., crystals e.g., nanocrystals) with hydrophobic internal surfaces and hydrophilic external surfaces are provided which form uniform, stable dispersions in a liquid (e.g., water) within which it is more thermodynamically favorable for liquid, e.g., water, to interact with other liquid (e.g., water) molecules in the bulk liquid phase than to fill the porous networks—leaving them dry and available to adsorb gas molecules (see, e.g., FIG. 4a). Exemplary gases include argon, oxygen, nitrogen, carbon dioxide, carbon monoxide, xenon, methane, helium, neon, and hydrogen.

[0055] The invention includes any particles, such as zeolites and metal—organic frameworks (MOFs), that can be synthesized with hydrophobic pore surfaces, e.g., in nanocrystalline form. The great range and variety of such materials makes these materials an advantageous—and highly tunable—platform to provide liquid (e.g., aqueous) solutions with permanent porosity. Moreover, solid powders of several hydrophobic zeolites and metal—organic frameworks, such as those described herein, can exclude liquid water from their internal pores at ambient pressure and temperature. For example, hydrostatic pressures in excess of 900 bar must be applied to force water into the pores of the pure-silica zeolite MFI (silicalite-1) at 25° C. This is because water intrusion into silicalite-1 (and other porous materials of the invention) is entropically disfavored since confined H.sub.2O molecules have less mobility than bulk H.sub.2O molecules and endothermic since surface—.sub.2O interactions are too weak to compensate for the hydrogen bonding interactions between H.sub.2O molecules that are lost during intrusion. Pressures of at least 200 bar are also required to force water into the pores of other pure-silica zeolites and hydrophobic zeolitic imidazolate frameworks (ZIFs). Porous particles of the invention may resist ingress of the liquid portion of the composition (e.g., water) up to applied pressures of about 1000 bar, e.g., up to about 1.5 bar, 2 bar, 5 bar, 10 bar, 20 bar, 50 bar, 75 bar, 100 bar, 150 bar, 200 bar, 300 bar, 400 bar, 500 bar, 600 bar, 700 bar, 800 bar, 900 bar, or 950 bar.

[0056] Although hydrophobic materials are not generally dispersible in polar solvents, particularly solvents such as water, pure-silica zeolites present a unique combination of hydrophobic internal pore surfaces templated by SiO.sub.4 tetrahedra, which prevents water intrusion, and hydrophilic external surfaces including terminal silanol groups, which promote water dispersibility for sufficiently small particles (FIG. 4c). With an internal surface area of 457 m.sup.2/g (839 m.sup.2/mL) and established routes to produce uniform nanocrystals of variable sizes (see, e.g., FIG. 10a and Table 4), silicalite-1 can generate aqueous solutions with permanent porosity and high gas capacities. Even though it does not contain any inherently strong gas adsorption sites, silicalite-1 adsorbs over 230 times the amount of O.sub.2 and 90 times the amount of CO.sub.2 in the solid state as can be dissolved in water at 1 bar and 25° C. on a volumetric basis (FIG. 8b) (see Table 8 for gravimetric basis). In addition, NMR experiments suggest that at least some fraction of silicalite-1 pores are accessible to hyperpolarized Xe in water.

[0057] The thermodynamic approach described here to designing porous liquids is generalizable to a wide range of hydrophobic porous materials. For instance, there are currently over 50 known pure-silica zeolites and many other high-silica zeolites that should be hydrophobic enough to exclude water in colloidal solutions. Beyond zeolites, metal-organic frameworks (MOFs) offer access to even higher internal surface areas and gas capacities, along with substantially more structural and chemical diversity. Most hydrophobic MOFs, however, have relatively hydrophobic external surfaces and are not inherently dispersible in water. Many hydrophobic MOFs are also prone to hydrolysis, particularly at low concentrations. This is true for the isostructural hydrophobic frameworks Zn(mIm).sub.2 (ZIF-8; where mIm=2-methylimidazolate, see, e.g., FIG. 1) and Co(mIm).sub.2 (ZIF-67) (FIGS. 1 and 4d), nanocrystals of which rapidly aggregate in water and may degrade if a large excess of water is present. Surface functionalization strategies can be applied to disperse and stabilize hydrophobic particles, e.g., MOFs, in a liquid, e.g., water, providing a route to aqueous MOF solutions with permanent porosity as long as surface ligands promote dispersibility without infiltrating—or blocking access to—the framework pores (see, e.g., FIGS. 10a and 10c). Surface functionalization may be noncovalent or covalent.

[0058] Noncovalent surface functionalization with macromolecules such as polyethylene glycol (PEG) represents one approach for dispersing nanocrystals in solvents that would otherwise induce aggregation and precipitation.

[0059] As an alternative to (or in addition to) synthetic polymers porous particles of the invention may include surface coatings of globular water-soluble proteins (e.g., albumins, e.g., serum albumins, e.g., bovine serum albumin (BSA), ovalbumin, lactalbumin, human serum albumin (HSA), etc.). Such macromolecules are advantageous for non-covalent surface (e.g., ZIF surface) functionalization due to their large size, rigidity, and propensity to adsorb on hydrophobic surfaces. BSA is useful for adsorbing onto ZIF-8 and ZIF-67 external surfaces because of its large diameter (˜7 nm) and 17 permanent disulfide linkages that minimize its conformational flexibility—the combination of which should sterically preclude protein intrusion into the ZIF framework and preserve permanent porosity.

[0060] The invention also provides covalent surface functionalization approaches to producing dispersible porous particles which offer the potential for strongly bound and precisely located surface ligands that promote water dispersibility at lower loadings than more weakly associated surface ligands (FIGS. 2a-2b). For covalent functionalization to lead to a porous aqueous liquid, the surface ligand must by hydrophilic enough—and present at a high enough density—to promote water dispersibility, while short enough or bulky enough to prevent pore infiltration. In addition, functionalization must be confined to the external surface of the particle (e.g., nanocrystal) and not inhibit gas accessibility to the internal pore surfaces. As an alternative approach, the invention provides mIm surface ligands that open epoxide rings and form a β-hydroxyalkyl covalent linkage to the ZIF surface (FIG. 4d). Other surface chemistries are known in the art.

Methods

[0061] The high gas capacities of the porous liquids reported here (see FIG. 17 and Tables 10-17) present intriguing possibilities for in vitro or in vivo gas, e.g., O.sub.2, delivery. Nature evolved intricate and tightly regulated systems to transport O.sub.2 in water over hundreds of millions of years, and it is challenging to deliver enough O.sub.2 to prevent hypoxia when these systems are absent or fail. A variety of natural and synthetic gas carriers—including cell-free hemoglobin, heme mimics, perfluorocarbon emulsions, and lipid- or polymer-coated microbubbles—have been explored to deliver O.sub.2 from aqueous fluids but overcoming issues that include limited gas-carrying capacity, poor control over release kinetics, lack of reversibility, large particle sizes, dose-limiting toxicity, and long-term stability remains an unsolved challenge. As a result, there are currently no FDA-approved injectable sources of O.sub.2 or artificial blood substitutes despite decades of research.

[0062] Compositions of the invention (e.g., silicalite-1 and ZSM-5) demonstrate surprisingly high oxygen carrying capacity compared to blood and other oxygen carrying liquids (e.g., Fluosol® and Oxygent™), as show in FIG. 7c. When oxygenated at 1 bar and 25° C., blood has an O.sub.2 carrying capacity near 23 mL/dL (15 g Hb/dL), which is an order of magnitude larger than the 2.9 mL/dL that can be dissolved in pure H.sub.2O. Among non-covalent O.sub.2 carriers, lipid-coated microbubble dispersions (90 vol %) have been demonstrated with irreversible O.sub.2 capacities that approach the gas-phase density of O.sub.2 (91 mL/dL), while concentrated perfluorocarbon emulsions (60 vol %) have reached reversible O.sub.2 capacities as high as 17 mL/dL (see FIG. 7c). Porous liquids offer a pathway to reversible O.sub.2 capacities that far exceed these values, which would allow larger amounts of O.sub.2 to be delivered from smaller volumes of an aqueous fluid. Since silicalite-1 and ZIF-8 nanocrystals adsorb 731 mL/dL and 241 mL/dL of O.sub.2, respectively, in the solid state, low-concentration aqueous solutions should be able to deliver exceptionally high densities of O.sub.2. Indeed, our 6.6 vol % solution of (mPEG)ZIF-8 nanocrystals has a measured O.sub.2 carrying capacity that is similar to many perfluorocarbon emulsions, which have concentrations of at least 20 vol %. Moreover, at a concentration of just 2.5 vol %, our silicalite-1 solution has a measured O.sub.2 capacity approaching that of blood. At a concentration of 12.5 vol %, this O.sub.2 carrying capacity increases to 89±10 mL/dL, which is comparable to the density of bulk O.sub.2 gas (FIG. 7c).

[0063] In addition to oxygen, other gases may be employed with the invention including argon, nitrogen, carbon dioxide, carbon monoxide, xenon, methane, helium, neon, or hydrogen. The compositions may be used to deliver or store any such gas for any appropriate purpose. For example, the compositions may be employed to increase volumetric mass transfer of a gas in a mass transfer limited process, e.g., catalysis, such as electrocatalysis.

[0064] Overall, these results show how to bring the high surface areas and gas capacities of porous solids to aqueous fluids. This approach has significant implications for biomedical and energy technologies, many of which are limited by the transport of gas molecules through aqueous environments. For instance, the porous water concept could lead to novel electrolytes that complement or replace gas diffusion electrodes in electrocatalysis or injectable sources of O.sub.2 that could serve as artificial blood substitutes, bridge therapies for hypoxia induced by trauma, sensitizers to make cancerous tumors more responsive to radiotherapy, or media for organ and tissue preservation. Though many factors beyond gas carrying capacity need to be considered in order to translate these systems to viable technologies, there are myriad possibilities for designing hydrophobic zeolites and MOFs with different crystal structures, nanocrystal sizes and shapes, and external surface functional groups to create porous water with high gas capacities and properties tailored to a specific application.

EXAMPLES

Example 1. Methods and Theory

Gas Adsorption Isotherms for Aqueous Colloidal Solutions

[0065] Free space measurements. Round-bottom glass sample tubes equipped with a Teflon-coated stir bar were attached to the instrument, and two temperature-controlled water baths were installed around the sample tube to control the sample and port temperatures. The sample tubes were evacuated, and the pressure transducers were then zeroed and scaled using the instrument software. Helium was dosed to the manifold to a pressure near 600 mbar, P.sub.dose, and the valve to the sample was then opened. The final He pressure (P.sub.He,final) was recorded after 1 min, and P.sub.dose/P.sub.He,final was used to calculate the volume of the empty tube (V.sub.s) according to Eqn 1.

[00001]$\begin{array}{cc}{V}_s=T_s\left(\frac{P_{dose}{V}_m}{P_{\mathrm{He},\mathrm{final}}{T}_m}-\frac{V_m}{T_m}-\frac{V_p}{T_p}\right)& \left(1\right)\end{array}$

[0066] After adding an aqueous solution to the tube and degassing (see below), a second iteration of the free space measurement was performed following the same dosing procedure, except for a longer wait time after opening the valve to the sample to allow the water vapor pressure to fully equilibrate. The final He partial pressure, P.sub.He,final, was obtained by subtracting the sample vapor pressure previously measured during degassing from the total pressure. The free space was then calculated using Eqn 1.

[0067] Degassing. To degas aqueous solutions, the pressure in the sample tube was decreased slowly through a servo valve while stirring at 250 rpm until the pressure was close to the expected vapor pressure, at which point the sample was briefly pulsed to the turbomolecular pump several times. Degassing was considered complete when the pressure was near the expected sample vapor pressure and did not noticeably rise between pulses of the turbomolecular pump. The sample vapor pressure was then recorded for future use.

[0068] Gas dosing and equilibration. Prior to the measurement of each gas absorption isotherm (see Tables 2 and 3), the aqueous solution was degassed following the procedure described above. Then, O.sub.2 or CO.sub.2 was dosed to the gas manifold of the 3Flex. The manifold dose pressure (P.sub.dose) required to reach a target final partial pressure (P.sub.gas) was estimated from

[00002]$\begin{array}{cc}{P}_{gas}=\frac{\frac{P_{dose}{V}_m}{R{T}_m}}{\frac{1}{R}\left(\frac{V_m}{T_m}+\frac{V_p}{T_p}+\frac{V_s}{T_s}\right)+k_{H,H_{2}O}{V}_{H_{2}O}+k_{H,\mathrm{np}}{V}_{\mathrm{np}}}& \left(2\right)\end{array}$

where R is the universal gas constant, V.sub.m is the volume of the manifold, V.sub.p is the volume of the sample port, k.sub.H,H.sub.2.sub.O is the Henry's constant for the gas solubility in water in units of mmol/L.Math.mbar, V.sub.H.sub.2.sub.O is the volume of water in the sample, k.sub.H,np is the Henry's constant for gas adsorption in the zeolite or ZIF nanocrystals as determined from solid-state isotherms, V.sub.np is the volume of nanocrystals in solution, and T.sub.m, T.sub.p, T.sub.s are the temperatures of the manifold, port, and sample, respectively.

[0069] When gas was dosed from the manifold to the sample by opening the sample valve, was is absorbed by the aqueous solution, and water was evaporated into the manifold simultaneously. Crucially, both processes must be allowed to reach equilibrium to record the true final partial pressure of the analysis gas and to accurately determine the amount of gas absorbed. As described below, absorption occurred much faster than water vapor equilibration for all solutions measured in this work. Typically, after equilibrium was reached, the sample valve was closed, and the manifold volume was evacuated. Then, the same gas was dosed to the manifold at a higher pressure and then the gas was dosed from the manifold to the sample.

[0070] Fitting equilibration data. When a fully or partially degassed solution is exposed to a higher gas pressure, the pressure above the sample will initially decrease as gas is adsorbed. Simultaneously, water will evaporate from the sample into the previously dry manifold volume. While the adsorption process was a relatively rapid process for all samples measured in this work, the water equilibration process was slow. By assuming that the source of water vapor is infinite and that the greatest rate-limiting factor is the constricted volume of the manifold, the equilibration process can be modeled by integrating the Sampson flow with respect to time as

P.sub.m(t)=a+be.sup.ct  (3)

where a, b, and c are constants that depend on initial sample pressure, viscosity, and the volume of constriction. From Eqn 3, we can approximate that water equilibration follows a pseudo-first order rate law that depends on the initial sample vapor pressure. As gas sorption can also be well-described with a pseudo-first order rate law, the entire process can be approximated as

[00003]$\begin{array}{cc}P\left(t\right)=A_{ad}{e}^{-t/t_{\mathrm{ad}}}+A_{C{O}_2}{e}^{-t/t_{{\mathrm{CO}}_2}}+A_{eq}{e}^{-t/t_{\mathrm{eq}}}+P_f& \left(4\right)\end{array}$

where A.sub.ad is a pressure-dependent factor for the adsorption-dominated region, t.sub.ad is the rate constant associated with the adsorption-dominated process, A.sub.CO.sub.2 is a pressure-dependent factor for the absorption of CO.sub.2 in water, t.sub.Co.sub.2 is the rate constant associated with CO.sub.2 absorption in water, A.sub.eq is a pressure-dependent factor for the water equilibration region, t.sub.eq is the rate constant associated with the water evaporation process, and P.sub.f is the expected final equilibration pressure for the system. Note that A.sub.CO.sub.2 and t.sub.CO.sub.2 were omitted for O.sub.2 measurements. The resulting fits to raw pressure vs time data were used to determine the final equilibration pressure for each isotherm point (see, Tables 10-12, and FIGS. 14a-14c).

[0071] Calculation of amount absorbed. After equilibrium is reached, the excess amount of gas absorbed by the solution can be calculated using

[00004]$\begin{array}{cc}{n}_{ads}=\frac{P_{dose}{V}_m}{R{T}_m}-P_{gas}\left(\frac{1}{R}\right)\left(\frac{V_m}{T_m}+\frac{V_p}{T_p}+\frac{V_s}{T_s}\right)& \left(5\right)\end{array}$

where P.sub.dose is the pressure dosed to the manifold and P gas is the final partial pressure of O.sub.2 or CO.sub.2.

[0072] When a gas has been dosed to the solution multiple times without degassing, the previous amount of gas adsorbed (n.sub.ads,i) and in the bulk gas phase inside the sample tube must be accounted for using

[00005]$\begin{array}{cc}{n}_{\mathrm{ads},\mathrm{tota1}}=\frac{P_{dose}{V}_m}{R{T}_m}+P_{\mathrm{gas},1}\left(\frac{1}{R}\right)\left(\frac{V_p}{T_p}+\frac{V_s}{T_s}\right)+n_{\mathrm{ads},1}-P_{\mathrm{gas},2}\left(\frac{1}{R}\right)\left(\frac{V_m}{T_m}+\frac{V_p}{T_p}+\frac{V_s}{T_s}\right)& \left(6\right)\end{array}$

where P.sub.gas,2 is the new equilibrium partial pressure of sorbent gas and n.sub.ads,total is the total moles of gas absorbed. The values for P.sub.gas,1 and P.sub.gas,2 are both obtained from fitting pressure vs time data as described above.

Oxygen Release Measurements in Deoxygenated Water

[0073] Due to the design of the electrode, two temperature compensations were required for each mg/L reading. The first of these was a solubility correction, accounting for differences in the equilibrium mg/L corresponding to the same pO.sub.2 at different temperatures. This was required to account for small difference between the measurement and calibration temperature over time (generally 1-4° C.). The following equation was used to perform this correction:

[00006]$\begin{array}{cc}{\left({cO}_2\right)}_{\mathrm{comp}}={\left({cO}_2\right)}_{meas}*\frac{H_{T_{meas}}}{H_{T_{\mathrm{cal}}}}& \left(7\right)\end{array}$

where cO.sub.2 is given in units of mg/L, (cO.sub.2)comp and (cO.sub.2).sub.meas correspond to the compensated and measured cO.sub.2, respectively, and H.sub.Tmeas and H.sub.Tcal correspond to the Henry's constants of water at the temperature of the measurement and the temperature of the calibration, respectively.

[0074] A second temperature compensation was also required due to the effects of temperature on the signal of the amperometric sensor. This correction, given by the manufacturer and applicable in the range where the measured temperature is within ±3° C. of the calibration temperature, is given by

(cO.sub.2).sub.comp=(cO.sub.2).sub.meas*A.sup.T.sup.cal.sup.−T.sup.meas.sup.)  (8)

where A is a temperature compensation constant (calibrated by the manufacturer and equal to 1.0176 for the sensor used in all measurements reported here). Note that these temperature corrections were only performed for the final mg/L readings, as initial O.sub.2 concentrations in deoxygenated solution were within error of the baseline.

[0075] Control experiments were conducted by injecting nitrogenated aqueous solutions of porous nanocrystals into deoxygenated water (Table 18). In all control experiments, there were negligible changes to the measured O.sub.2 concentration in deoxygenated water, confirming that no external sources of O.sub.2 were introduced during the injection.

[0076] The amount of oxygen released from aqueous solutions of zeolite and MOF nanocrystals to deoxygenated water was calculated by:

n.sub.delivered=n.sub.water,f−(n.sub.water,i−n.sub.water,ejected)  (9)

where n.sub.water,f is the moles of O.sub.2 in bulk water after injection, n.sub.water,i is the moles of O.sub.2 initially in the deoxygenated bulk water. Since the vial has a fixed volume and begins filled with deoxygenated water, the injection of a known volume of dispersion leads to the ejection of a corresponding volume of deoxygenated water, whose total moles of O.sub.2 is denoted by n.sub.water,ejected. Using the compensated cO.sub.2 values, this calculation becomes:

O.sub.2,delivered=V.sub.H.sub.2.sub.O,f(cO.sub.2).sub.f,comp−cO.sub.2.sub.i(V.sub.H.sub.2.sub.O,i−V.sub.inj)  (10)

Where O.sub.2,delivered is the amount of O.sub.2 in μg, (cO.sub.2).sub.f,comp , comp is the compensated final cO.sub.2 after injection, expressed in mg/L, V.sub.H.sub.2.sub.O,f is the final volume of bulk H.sub.2O after injection in mL, V.sub.inj is the volume of injection in mL, V.sub.H.sub.2.sub.O,i is the initial volume of bulk H.sub.2O before injection in mL, and cO.sub.2.sub.i is the initial concentration of O.sub.2 in the vial.

[0077] To calculate the total O.sub.2 carrying capacity of the dispersion, one must also consider the amount of O.sub.2 remaining inside the pores of the nanocrystals at the final pO.sub.2 to which the system is equilibrated. For this, one must first find O.sub.2, delivered,NC, the amount of O.sub.2 delivered by the nanocrystals alone. Since the total delivered O.sub.2 (in μg) is the sum of the O.sub.2 delivered by the nanocrystals and that delivered by the water in the dispersion, rearranging this sum yields:

O.sub.2,delivered,NC=O.sub.2,delivered−χ.sub.H.sub.2.sub.OV.sub.injH.sub.H.sub.2.sub.O,oxρH.sub.2.sub.O,oxpO.sub.2,ox×31999  (11)

where the last term corresponds to the O.sub.2 delivered by the water in the dispersion, and where χ.sub.H.sub.2.sub.O is the volumetric fraction of water in the injected dispersion, ρ.sub.H.sub.2.sub.O,ox is the density of water at the oxygenation temperature of the dispersion prior to addition in g/mL, H.sub.H.sub.2.sub.O,ox is the Henry's constant of the water at the oxygenation temperature in mmol/g/bar, and pO.sub.2,ox is the partial pressure of O.sub.2 at which the dispersion was oxygenated in bar (0.2 bar for air-equilibrated samples and 1 bar for samples equilibrated with pure O.sub.2).

[0078] With this value, one can now find the amount of O.sub.2 remaining in the nanocrystals. By assuming that all experiments are performed in the Henry regime (namely, that the amount of O.sub.2 adsorbed has a linear dependence on pressure, which is confirmed by the solid-state adsorption data), the total O.sub.2 in the nanocrystals of the dispersion is equivalent to:

[00007]$\begin{array}{cc}{O}_{2,\mathrm{total},\mathrm{NC}}=\frac{O_{2,\mathrm{delivered},\mathrm{NC}}}{\left({pO}_{2,ox}-{pO}_{2,f}\right)}{pO}_{2,\mathrm{ox}}& \left(12\right)\end{array}$

where pO.sub.2,f is the final pO.sub.2 of the system in bar.

[0079] Combining with the O.sub.2 delivered by the water in the injected dispersion, one can calculate the total O.sub.2 carrying capacity of the aqueous solution, C.sub.O2, in mL per dL as:

[00008]$\begin{array}{cc}{C}_{O_2}={pO}_{2,\mathrm{ox}}\left(\frac{O_{2,\mathrm{delivered},\mathrm{NC}}}{\left({pO}_{2,\mathrm{eq}}-{pO}_{2,f}\right)}+{\chi }_{H_{2}O}{V}_{\mathrm{inj}}{H}_{H_{2}O,\mathrm{eq}}{\rho }_{H_{2}O,\mathrm{eq}}\right)\times \frac{22.414}{31.999}\times 100& \left(13\right)\end{array}$

[0080] To calculate the % of theoretical capacity for each aqueous solution, the following equation was used:

[00009]$\begin{array}{cc}\frac{O_{2,\mathrm{delivered},\mathrm{NC}}}{O_{2,\mathrm{theoretical},\mathrm{NC}}}\times 100\%& \left(14\right)\end{array}$

where O.sub.2,theoretical,NC is the theoretical amount of O.sub.2 released by the nanocrystals in the aqueous solution, with both parameters above given in terms of μg O.sub.2.

[0081] Here, O.sub.2, theoretical,NC can be calculated from solid-state O.sub.2 adsorption isotherms (see FIGS. 11a-11d, 21a-21b, and 24a-24c, and Table 5). Since the total O.sub.2 in the nanocrystals, as equilibrated at a pressure pO.sub.2,eq prior to injection, can be partitioned into the O.sub.2 that is released plus the O.sub.2 that remains adsorbed inside the nanocrystals, this can be rearranged to give:

O.sub.2,theoretical,NC=O.sub.2,NC,ox−O.sub.2,NC,adsorbed  (15)

Where O.sub.2,NC,ox is the amount of O.sub.2 in the starting solution, and O.sub.2, NC,adsorbed is the amount that remains inside the nanocrystals. Substituting known parameters for both of these variables yields:

O.sub.2,theoretical,NC=C.sub.NCV.sub.inj(H.sub.NC,eqpO.sub.2,ox−H.sub.NC,fpO.sub.c,f,calc)×31999  (16)

Where C.sub.NC is the concentration of nanocrystals in the dispersion in g/mLH.sub.NC,eq and H.sub.NC,f are the Henry's constants of the nanocrystal at the temperature the dispersion was oxygenated at and at the final temperature post-injection, respectively, and pO.sub.2,f,calc is the calculated partial pressure of O.sub.2 at the final temperature post-injection, respectively.

[0082] To calculate pO.sub.2,f,calc, the total number of moles of O.sub.2 in the final solution, n.sub.f, is given by:

n.sub.f=n.sub.NC,f+n.sub.H.sub.2.sub.O,f+n.sub.excess,adsorbed,f  (17)

where n.sub.NC,f is the final moles of O.sub.2 in the nanocrystals, n.sub.H.sub.2.sub.O,f is the final moles of O.sub.2 in the water, and n.sub.excess,adsorbed,f is any moles of O.sub.2 that are adsorbed by existing nanocrystals already present in the vial—this latter term is only needed in cases where multiple injections were performed sequentially into the same vial.

[0083] The final number of moles of O.sub.2 is equal to the initial moles of O.sub.2 present in water (n.sub.initial), plus the O.sub.2 injected (n.sub.injected) and the O.sub.2 already adsorbed in “previous” nanocrystals from previous injections still in the vial (n.sub.initial,NC,previous), minus the O.sub.2 ejected (n.sub.ejected):

n.sub.f=n.sub.NC,f+n.sub.H.sub.2.sub.O,f+n.sub.excess,adsorbed,f=n.sub.injected+n.sub.initial−n.sub.ejected+n.sub.initial,NC,previous  (18)

[0084] Note that for measurements performed using fresh deoxygenated water and no prior injections, the terms n.sub.excess,adsorbed,f and n.sub.initial,NC,previous are both zero.

[0085] Expanding each term:

n.sub.NC,f+n.sub.H.sub.2.sub.O,f+n.sub.excess,adsorbed,f=pO.sub.2,f(C.sub.NCV.sub.injH.sub.NC,f)+pO.sub.2,f(V.sub.H.sub.2.sub.O,fH.sub.H.sub.2.sub.O,fρ.sub.H.sub.2.sub.O,f)+pO.sub.2,f(H.sub.NC,fN.sub.NC,previous)  (19)

And

n.sub.injected+n.sub.initial−n.sub.ejected+n.sub.initial,NC,previous=V.sub.injpO.sub.2,eq(C.sub.NCH.sub.NC,eq+χ.sub.H.sub.2.sub.OH.sub.H.sub.2.sub.O,eqρH.sub.2.sub.O,eq)+pO.sub.2,iH.sub.H.sub.2.sub.O,iρH.sub.2.sub.O,i(V.sub.H.sub.2.sub.O,i−V.sub.ej)+H.sub.NC,eqpO.sub.2,eqN.sub.NC,previous  (20)

Where V.sub.H.sub.2.sub.O,f is the final volume of water in the measurement vial, ρ.sub.H.sub.2.sub.O,i and p H2of are the densities of water at the initial and final temperature, respectively, H.sub.H.sub.2.sub.O,i and H.sub.H.sub.2.sub.O,f are the Henry's constants of water (Table 7) at the initial and final temperature, respectively, N.sub.NC,previous is the amount of nanocrystals still in the vial from prior injections (expressed in g).

[0086] Setting these two expressions equal, collecting terms, and solving for pO.sub.2,f yields:

[00010]$\begin{array}{cc}{pO}_{2,f}=\frac{V_{\mathrm{inj}}{pO}_{2,\mathrm{eq}}\left({\chi }_{\mathrm{NC}}{H}_{\mathrm{NC},\mathrm{eq}}+{\chi }_{H_{2}O}{H}_{H_{2}O,\mathrm{eq}}{\rho }_{H_{2}O,\mathrm{eq}}\right)+H_{\mathrm{NC},\mathrm{eq}}{pO}_{2,\mathrm{eq}}{N}_{\mathrm{NC},\mathrm{previous}}}{\left({\chi }_{NC}{V}_{\mathrm{inj}}{H}_{\mathrm{NC},f}+V_{H_{2}O,f}{H}_{H_{2}O,T_f}{\rho }_{H_{2}O,T_f}+H_{\mathrm{NC},f}{N}_{\mathrm{NC},\mathrm{previous}}\right)}+\frac{{pO}_{2,i}{H}_{H_{2}O,i}{\rho }_{H_{2}O,i}\left(V_{H_{2}O,i}-V_{\mathrm{ej}}\right)}{\left({\chi }_{NC}{V}_{\mathrm{inj}}{H}_{\mathrm{NC},f}+V_{H_{2}O,f}{H}_{H_{2}O,T_f}{\rho }_{H_{2}O,T_f}+H_{\mathrm{NC},f}{N}_{\mathrm{NC},\mathrm{previous}}\right)}& \left(21\right)\end{array}$

[0087] This pO.sub.2,f can then be used in Eqn 16 for calculating the theoretical O.sub.2 delivery for the nanocrystals in the dispersion.

Oxygen Release Measurements in Packed Red Blood Cells (See Tables 19-27)

[0088] Blood gas and co-oximetry (CO-ox) data were obtained using a Radiometer ABL 90 Co-Ox Flex. Citrate-buffered packed red blood cells from donated human blood (hemoglobin, ˜7 g/dL; pH 7.1; T=25° C.) was first desaturated under flowing 95:5 N.sub.2/CO.sub.2 to an oxyhemoglobin saturation of 0-10%. Baseline hemoglobin, blood gas, and CO-ox values were measured prior to sample addition. Gas chromatography vials (2 mL) each fitted with a septa cap and stir bar were filled with 2 mL of deoxygenated blood. For a given measurement, a colloidal solution (stored under O.sub.2 or N.sub.2) was drawn into a glass syringe. During addition to the blood, a vent syringe was added to the vial to allow the excess blood displaced by the sample volume to exit. Both needles were removed, and the vial was stirred for 5 min prior to a CO-ox measurement. As a secondary control, the above experimental procedure was repeated using 5% dextrose (absent any nanocrystals).

[0089] The amount of O.sub.2 delivered to the packed red blood cells was calculated by:

[00011]$\begin{array}{cc}\mathrm{Vol}\mathrm{of}{O}_2\left(\mathrm{mL}\right)=\left[\left(\frac{1.39\mathrm{mL}{O}_2}{g{O}_2\mathrm{Hb}}\times \mathrm{ct}\mathrm{Hb}\times {FO}_2\mathrm{Hb}\right)+\left(0.0039{PO}_2\right)\right]\times \mathrm{dL}\mathrm{blood}& \left(22\right)\end{array}$

where 1.39 mL O.sub.2/g O.sub.2Hb is the gravimetric O.sub.2 capacity of fully saturated oxyhemoglobin (O.sub.2Hb), ctHb is the total hemoglobin count in g/dL blood, FO.sub.2Hb is the fraction of oxyhemoglobin to total hemoglobin expressed as a percentage, and 0.0039 mL O.sub.2/mmHg/dL blood is the Henry's constant for O.sub.2 solubility in blood at 25° C. The first term of the equation represents the O.sub.2 bound to hemoglobin, while the second term represents the dissolved O.sub.2 in the blood.

[0090] The equilibrated pO.sub.2 after most sample injections was below the lower detection limit of the instrument used in this study (31.1 mmHg). Since pO.sub.2 is needed to determine the dissolved oxygen content, an estimated pO.sub.2 was calculated. Under standard conditions (T=37° C., pH=7.4, and pCO.sub.2=40 mmHg), the relationship between pO.sub.2 and SO.sub.2 is well described by the oxyhemoglobin dissociation curve (ODC). It is thus possible to use SO.sub.2 to calculate pO.sub.2 with the aid of empirically derived algorithms based upon the ODC. For clarity, we denote the thus-obtained value as (pO.sub.2)° .sub.c where the subscript denotes that it is calculated and the superscript denotes that it is at physiological “standard state” (T=37° C., pH=7.4, and pCO.sub.2=40 mmHg). Since the ODC changes heavily upon deviation from physiological conditions, the pO.sub.2 calculated must be adjusted for changes in temperature, pH, and pCO.sub.2 using an appropriate model. The Severinghaus model was chosen due to its good agreement with pO.sub.2 values for certain samples that were above the detection limit of the blood gas instrument. The equation used is Severinghaus' empirical modification of Hill's equation, given by:

(pO.sub.2)° .sub.c=e.sup.0.385 ln(S.sup.−1.sup.−1)+3.32−(72S).sup.−1.sup.−0.175S.sup.−6  (23)

[0091] Here, S=SO.sub.2=(FO.sub.2Hb)/(FO.sub.2Hb+FHHb), expressed as a fraction between 0 and 1. To convert each (pO.sub.2)° .sub.c to a (pO.sub.2).sub.c at each given pH, T, and pCO.sub.2, Kelman's equation was used:

(pO.sub.2).sub.c=(pO.sub.2)° .sub.c*10.sup.−(0.024(37−T)+0.40(pH−7.0)+0.06(log(40)−log(pCO.sup.2.sup.)))  (24)

Where T is the temperature in ° C. and pCO.sub.2 is the CO.sub.2 partial pressure in mmHg. For samples where the pCO.sub.2 was below detection limit, the pCO.sub.2 correction term was omitted. Furthermore, it should be noted that even the largest ΔpO.sub.2 possible in our calculations (assuming the true pO.sub.2 was far below the detection limit near 0) would only lead to a 1-2% deviation in the calculated amount of O.sub.2 delivered.

[0092] For each calculation of the amount of O.sub.2 released, a background correction was also applied based on nitrogenated control experiments for analogous aqueous solutions. Upon determining an average O.sub.2 background, this value was then subtracted from the average O.sub.2 delivered at each dose (50, 100, or 150 μL) to obtain the final value for the average O.sub.2 delivered at that dose. The nitrogen controls displayed minimal O.sub.2 backgrounds (3% average increase in FO.sub.2Hb for silicalite-1, and 5% average increase in FO.sub.2Hb for (mPEG)ZIF-8). Among all measurements, only the oxygenated nanocrystal dispersions displayed linear correlations between the measured O.sub.2 delivered and the injection dose; both the nitrogenated controls did not show linear correlations as expected. Furthermore, the average O.sub.2 carrying capacity (4 mL/dL) of the 5% dextrose dispersion was very close to the theoretical value (approximately 3 mL/dL).

[0093] To obtain an average O.sub.2 carrying capacity for each of the dispersions, the dose volume in μL was plotted versus the average volume of O.sub.2 delivered in μL for each of the three doses. The slope of the linear best-fit line for each dispersion, multiplied by 100, yielded the calculated O.sub.2 carrying capacity in mL/dL.

Calculating Extent of mPEG Surface Functionalization and Grafting Density

[0094] To calculate the extent of surface functionalization with mPEG, ZIF-8 nanocrystals were approximated as spheres. Given the size of the nanocrystal and the dimensions of the unit cell, the number of unit cells at the surface was calculated as:

[00012]$\begin{array}{cc}{N}_{\mathrm{surface}}=\frac{S{A}_{nc}}{A_{\mathrm{unit}\mathrm{cell}}}& \left(25\right)\end{array}$

where N.sub.surface is the number of unit cells at the surface of the bulk nanocrystal, SA.sub.nc is the surface area of the nanocrystal, and A.sub.unit cell is the area for a single face of the ZIF-8 unit cell.

[0095] From the number of unit cells at the surface, the total number of surface mIm linkers were obtained as:

mIm.sub.surface=N.sub.surface×mIm.sub.single unit cell  (26)

where mIm.sub.surface is the number of surface-terminating mIm linkers and mIm.sub.single unit cell is the number of surface-terminating mIm linkers in a single unit cell obtained from the crystal structure of ZIF-8.

[0096] For surface-selective functionalization, the maximum theoretical number of mPEG ligands at the surface should be equivalent to mIm.sub.surface. Thus, the extent of surface functionalization can be calculated as:

[00013]$\begin{array}{cc}\%\mathrm{functionalization}=\frac{\%\mathrm{mPEG}}{\%{\mathrm{mIm}}_{\mathrm{surface}}}& \left(27\right)\end{array}$

where % mPEG is the % mPEG ligand relative to that of the mIm linker present based on digestion NMR (FIG. 26), and % mIm.sub.surface is the % surface-terminating mIm linker relative to that of the total mIm linker calculated based on the size of the nanocrystal.

[0097] From the extent of functionalization, the number of mPEG ligands present in a single nanocrystal can be calculated by multiplying mIm.sub.surface by % functionalization. The surface grafting density can then be calculated as:

[00014]$\begin{array}{cc}\mathrm{grafting}\mathrm{density}=\frac{N_{mPEG}}{S{A}_{\mathrm{nc}}}& \left(28\right)\end{array}$

where N.sub.mPEG is the number of mPEG ligands grafted to a single nanocrystal.

Theoretical Density Calculations

[0098] Theoretical solution densities were calculated in order to compare to experimental values (FIGS. 5a-5b and FIGS. 8a-8u). The solution density is the sum of 3 individual mass-per-volume concentrations: 1) bulk fluid outside the pores, 2) porous nanoparticles, and 3) fluid inside the nanocrystal pores. Specifically,

ρ.sub.solution=ρ.sub.fluid,bulk(1−c.sub.np)+ρ.sub.npc.sub.np+ρ.sub.fluid,poreV.sub.poreρ.sub.npc.sub.np  (29)

where ρ.sub.solution is the solution density in g/mL, ρ.sub.fluid,bulk is the density of the bulk fluid (e.g. water or 5% dextrose solution), c.sub.np is the volumetric concentration of the nanoparticle solution, ρ.sub.np is the crystallographic density of the nanoparticle, ρ.sub.fluid,pore is the density of the fluid inside the pores, and V.sub.pore is the pore volume. Note that the crystallographic density of the nanoparticle must be used in order to account for both the volume occupied by the nanoparticle framework and the volume occupied by the pores. The crystallographic densities of each material are listed in Table 1. The concentration of nanoparticle in solution (c.sub.np) is calculated as described above. Lastly, the pore volume (V.sub.pore) was obtained from a t-plot analysis of BET isotherms for each material (FIGS. 12a-12d).

[0099] For PEG/ZIF-67 and BSA/ZIF-67 solutions, the density of aqueous PEG or BSA solutions at the relevant concentration was used as ρ.sub.fluid,bulk. The relevant concentration of the aqueous PEG solution was calculated per total volume of colloidal solution because PEG is sterically capable of accessing the entire pore volume of the nanocrystal, while the relevant concentration of the aqueous BSA solution was calculated per volume of water because BSA is too sterically restricted to access the internal pore volume.

Internal and External Surface Area in the Solid State

[0100] Solid-state adsorption measurements of nanocrystalline powders include contributions from adsorption in the internal pores of a sample, as well as on external surfaces and interparticle voids. We assessed the relative amount of external surface area in our samples via the t-plot method for P/P.sub.0>0.3 using the Harkins and Jura thickness curves (FIG. 12a-12e). For silicalite-1, we also validated this analysis by calculating the external surface area of a non-calcined sample, which has no internal porosity (FIG. 12e). Both the t-plot method and the comparison of calcined vs. non-calcined samples indicate that 16-18% of the total measured surface area in the solid state is due to external surfaces that would be covered by water in aqueous solution.

Example 2

[0101] To create uniform, stable dispersions of silicalite-1 in water and to determine if any permanent porosity is present, we first optimized synthesis, purification, and calcination conditions to form nanocrystals of similar size (average diameter=60±X nm or 90±16 nm) (FIG. 16b) and to remove structure-directing tetrapropylammonium cations from the zeolite pores without irreversibly aggregating the particles in the solid state. The resulting silicalite-1 nanocrystals yielded translucent aqueous colloidal solutions that were exceptionally stable (FIG. 15a), with no settling or aggregation observed over the course of at least several weeks (FIGS. 4e and 15a). Moreover, colloidal stability was not impacted by degassing the solutions under vacuum. If the porous networks of the silicalite-1 nanocrystals in these solutions do not contain water, the most concentrated colloidal solution would be 8.3% porous.

[0102] Since the volume occupied by a porous liquid with dry (e.g., gas-, e.g., air-filled) pores will be larger than the volume occupied by an equivalent nonporous liquid with wet (solvent-filled) pores, density measurements were used as an initial probe of the hydration status of silicalite-1 pores in aqueous dispersions. Surprisingly, experimental densities across a wide range of silicalite-1 concentrations are within 0.5% of the values predicted for dry pores at 15, 25, and 37° C. (FIGS. 5a and 8a-8f). This is in contrast to dispersions of silicalite-1 in ethanol—where intrusion of the less polar solvent molecules should be thermodynamically favored at ambient pressure—and of the hydrophilic zeolite LTL in water—where water intrusion into the more polar aluminosilicate pores should also be thermodynamically favored under ambient conditions—which both have densities consistent with nonporous liquids containing solvent-filled pores (FIGS. 5b and 8g-8l). Note that the density of solvent within a porous network can be as much as 40% lower than the bulk liquid density due to confinement effects.

[0103] For a porous liquid to be useful for gas storage and transport applications, the pore networks need to be not only dry but also capable of reversibly adsorbing and releasing gas molecules. To directly probe the gas accessibility of pores within aqueous dispersions of silicalite-1 nanocrystals, the amount of O.sub.2 and CO.sub.2 absorbed in degassed solutions was measured. At 25° C., the gas absorption capacity of a 12 vol % (20 wt %) solution of silicalite-1 nanocrystals was 26 mmol 02/L at 0.84 bar and 284 mmol COWL at 0.67 bar, which is over an order of magnitude more than the 1.1 mmol/L of O.sub.2 and 23 mmol/L of CO.sub.2 absorbed in water under the same conditions (FIGS. 6a and 6b, respectively). Moreover, these gas capacities are 88% and 86%, respectively, of the O.sub.2 and CO.sub.2 capacities predicted by assuming that solution absorption is equivalent to the sum of the pure-water gas solubility and the adsorption capacity of silicalite-1 nanocrystals in the solid state (FIG. 6c, see also see FIGS. 11a, 11b, 21a, 21b, 23a, 23b, and Table 6). Since the solid-state gas capacity measured for nanocrystalline powders will also include contributions from gas adsorption at external surfaces and in interparticle voids that will not be present in solution these gas capacities are consistent with dry porous networks in liquid water that are fully accessible to gas molecules. Solid state N.sub.2 adsorption isotherms at 25° C. for silicalite-1 are shown in FIGS. 22a-22b. Vol % concentrations of silicalite-1 and LTL zeolite were determined as described in Table 3.

[0104] Cycling experiments confirm that gas absorption is fully reversible upon degassing (FIG. 13). In addition, gas release can be directly quantified by measuring the change in dissolved O.sub.2 when a gas-loaded solution is added to pure, degassed water (see FIG. 7a). For example, when an oxygenated silicalite-1 dispersion is injected into deoxygenated water, a partial pressure gradient is established that drives the release of adsorbed O.sub.2 from the silicalite-1 nanocrystals into bulk water until a new equilibrium is established once the partial pressures of dissolved and adsorbed O.sub.2 are equal. Consistent with the absorption experiments, oxygenated silicalite-1 solutions deliver up to 89% of their predicted O.sub.2 capacity to deoxygenated water (see FIG. 7b). Moreover, the amount of dissolved O.sub.2 equilibrates within seconds after injection of a silicalite-1 dispersion, which demonstrates the rapid O.sub.2 release kinetics of these porous liquids. In contrast to silicalite-1, the amount of O.sub.2 and CO.sub.2 absorbed in an aqueous dispersion of zeolite LTL nanocrystals is nearly identical to pure water and corresponds to about 0% of the zeolite capacity predicted for dry pores (FIG. 7b). These results emphasize the importance of hydrophobic pores and permanent porosity to achieving high gas capacities in water.

Example 3

[0105] PEG (M.sub.n=35,000 g/mol) at 30 wt % in water can disperse 20 wt % (21 vol %) of ZIF-8 (average size=91±8 nm) and 7.0 wt % (7.4 vol %) of ZIF-67 (average size=780±14 nm) without observable aggregation (FIGS. 2a-2b and 3a-3b). Furthermore, ZIF-8 remains crystalline when associated with PEG in water for at least 5 weeks, and PEG increases the hydrolytic stability of ZIF-67, which otherwise rapidly degrades in water (FIGS. 15d-15e). However, the O.sub.2 capacities of the aqueous PEG dispersions of ZIF-8 and ZIF-67 are less than 11% of the theoretical capacities (FIG. 7b). Along with density measurements (FIG. 5b), this limited O.sub.2 capacity suggests that these aqueous solutions are not porous because of PEG intrusion into the ZIF pores. Given that PEG is a compact, flexible polymer and is amphiphilic, there does not appear to be a strong enough driving force to prevent its intrusion by either sterics or thermodynamics—an effect that has been observed in the solid state for PEG with other metal—organic frameworks. DLS measurements of colloidal solutions of PEG/ZIF-8 and PEG/ZIF-67 in water are shown in FIGS. 25a-25b.

[0106] Mixing BSA (10 wt %) with ZIF-67 nanocrystals (3.8 wt %) enables complete dispersion of ZIF-67 in water with no observable precipitation over a period of at least 4 days (FIGS. 8f, 15d-15e, and 16g). Density measurements on BSA/ZIF-67 dispersions are consistent with air-filled pores (FIG. 5a). Moreover, when oxygenated BSA/ZIF-67 dispersions are injected into deoxygenated water, the measured O.sub.2 capacity approaches 80%±9% of the theoretical capacity obtained by assuming all ZIF-67 pores are empty and accessible to gas (FIG. 7b). Furthermore, the O.sub.2 capacity of the BSA/ZIF-67 dispersion does not change after 4 days in water, as the adsorbed BSA corona presumably protects ZIF-67 from hydrolytic degradation via surface passivation. Similar O.sub.2 capacities are also obtained for BSA/ZIF-8 dispersions (Table 17). Thus, non-covalent protein adsorption successfully extends the porous water concept to hydrophobic MOFs.

[0107] ZIF-8 nanocrystals were reacted with methoxypolyethylene epoxide (mPEG; M.sub.n=750 g/mol for PEG). The formation of the expected covalent linkage between ring-opened epoxide and mIm was confirmed by mass spectrometry (FIG. 27), with NMR digestion experiments indicating that approximately 14% of the mIm surface ligands are functionalized with mPEG (FIG. 26). Importantly, this grafting density (1.2 ligands per nm.sup.2) was sufficient to stabilize colloidal dispersions of ZIF-8 in water at up to 8.3 vol % (7.0 wt %), with minimal precipitation or aggregation over the course of at least 5 days (FIGS. 8e and 15b). In contrast to ZIF-8 nanocrystals non-covalently functionalized with PEG, the solution density as a function of concentration is consistent with that expected for a porous liquid containing air-filled pores (FIG. 5a), and the measured O.sub.2 release upon injection of an oxygenated dispersion into deoxygenated water is 96%±7% of the theoretical capacity (FIG. 7b). This demonstrates that localization of short hydrophilic ligands on the surface of hydrophilic MOF nanocrystals can impart dispersibility in water while maintaining permanent porosity and a high gas absorption capacity. Solid-state adsorption isotherms for ZIF-8 nanocrystals before and after functionalization with mPEG (FIGS. 24a-24c), show that covalent functionalization has a negligible impact on the adsorption of O.sub.2 and N.sub.2 near ambient temperature.

Example 4

[0108] Nanocrystals of the zeolite ZSM-5—which is the isostructural aluminosilicate analogue of silicalite-1—have more hydrophilic external surfaces than silicalite-1 nanocrystals (FIG. 10b) and can form aqueous solutions at a concentration as high as 39 vol % (FIG. 15c) with a viscosity of only 57 cP at 25° C. for a 39 vol % solution (see silicalite-1 viscosity vs vol % in FIG. 9). At a high Si:Al ratio of 64, density measurements indicate that the pores of ZSM-5 nanocrystals (average diameter=238±23 nm) (FIG. 16d) are hydrophobic enough to prevent water intrusion and form a porous solution (FIG. 8s-8u). As a result, our 39 vol % solution of ZSM-5 nanocrystals has an extremely high O.sub.2 carrying capacity of 187±18 mL/dL that far exceeds the capacity of any other natural or synthetic aqueous O.sub.2 carrier (FIG. 7c).

[0109] As an initial exploration of whether the high O.sub.2 capacities of these porous liquids could be translated to more biomedically relevant environments than pure water, we performed ex vivo experiments to test the delivery of O.sub.2 to deoxygenated donated human blood. Importantly, density measurements confirm that the permanent porosity of aqueous silicalite-1 and (mPEG)ZIF-8 dispersions is maintained in a 5% dextrose solution (FIGS. 8d-8f and 8p-8r), which is isotonic to red blood cells (RBCs). The O.sub.2 carrying capacity of these solutions can be extracted from measurement of the change in oxyhemoglobin concentration upon addition of different volumes of solution to deoxygenated RBCs. Notably, oxygenated solutions of 90-nm silicalite-1 nanocrystals (10.8 vol %), 60-nm silicalite-1 nanocrystals (9.1 vol %), and (mPEG)ZIF-8 (6.7 vol %) in 5% dextrose rapidly release O.sub.2 after injection into RBCs—with the amount of O.sub.2 released increasing linearly in a dose-dependent manner—yielding O.sub.2 carrying capacities that are in excellent agreement with the values predicted from adsorption measurements and O.sub.2 release experiments in pure water (FIGS. 7d and 20a-20b). Additionally, more concentrated silicalite-1 dispersions were capable of delivering 110 mL/dL of O.sub.2 to RBCs—well above the density of bulk O.sub.2 gas.

Example 5

[0110] The following tables provide further characteristics of the compositions of the invention.

TABLE-US-00001 TABLE 1 Crystallographic densities. Crystallographic Density Material (g/mL) silicalite-1 1.858 ZSM-5 (Si/Al = 64) 1.880 LTL 1.959 ZIF-8 0.95 ZIF-67 0.947

TABLE-US-00002 TABLE 2 Weight % remaining as a function of temperature determined by TGA for zeolite samples. Samples were dropcast into TGA pans and dried in air before beginning the TGA run. The drop in mass corresponds to the amount of re-adsorbed water in the zeolite, which was taken into account when determining the concentrations of aqueous solutions by TGA or manual drying and weighing. Temperature Wt % Material (° C.) remaining silicalite-1 (90 nm) 150 97.3110 200 97.2128 250 97.1162 silicalite-1 (60 nm) 150 95.2452 200 95.1167 250 95.0153 LTL 150 86.3378 200 85.9571 250 85.8689 ZSM-5 (Si/Al = 64) 150 94.9425 200 94.7085 250 94.5540

TABLE-US-00003 TABLE 3 Zeolite solution concentrations for samples used in absorption isotherm measurements were determined by ICP, TGA, and manual dryingand weighing, which all give consistent results. Concen- Concen- Concentration tration tration from manual from ICP from TGA weighing Material Sample (vol %) (vol %) (vol %) silicalite-1 before absorption 12.0 11.9 11.98 (90 nm) experiments after absorption 11.8 experiments before cycling 9.67 9.05 9.830 absorption experiments after cycling 9.83 9.736 absorption experiments LTL before absorption 5.27 4.78 5.367 experiments after absorption 4.82 5.034 experiments

TABLE-US-00004 TABLE 4 Summary of BET surface areas and pore volumes for materials studied in this work obtained from 77K N.sub.2 adsorption isotherms. BET Pore surface volume area at P/P.sub.0 = 0.1 Material (m.sup.2/g) (mL/g) silicalite-1 457.2 0.18 LTL 512.9 0.21 ZIF-8 1749 0.67 (mPEG)ZIF-8 1674 0.65 ZIF-67 1768 0.68

TABLE-US-00005 TABLE 5 Summary of linear fits to solid-state O.sub.2 and N.sub.2 adsorption data and Henry's law constants used ins calculations of theoretical solution capacities. Henry's constants in mmol/L .Math. mbar are calculated using the crystallographic density of the material (Table 1). T Slope Intercept Henry's constant Material (° C.) Gas (mmol/g .Math. mbar) (mmol/g) (mmol/L .Math. mbar) silicalite-1 15 O.sub.2 2.016 × 10.sup.−4 0.0019 0.3705 (calcined) 25 O.sub.2 1.656 × 10.sup.−4 0.0017 0.3044 37 O.sub.2 1.329 × 10.sup.−4   8.216 × 10.sup.−4 0.2443 25 N.sub.2 1.804 × 10.sup.−4 0.00168 0.3316 silicalite-1 25 O.sub.2 8.408 × 10.sup.−6 −5.884 × 10.sup.−4 0.0155 (non-calcined) LTL 15 O.sub.2 8.937 × 10.sup.−5 −6.131 × 10.sup.−5 0.1751 25 O.sub.2 7.464 × 10.sup.−5   2.151 × 10.sup.−4 0.1462 37 O.sub.2 6.174 × 10.sup.−5 −2.862 × 10.sup.−4 0.1209 25 N.sub.2 1.286 × 10.sup.−4   8.276 × 10.sup.−4 0.2519 ZIF-8 15 O.sub.2 1.215 × 10.sup.−4 −3.682 × 10.sup.−4 0.1154 25 O.sub.2 1.054 × 10.sup.−4 −3.448 × 10.sup.−4 0.1001 37 O.sub.2 8.659 × 10.sup.−5 −6.832 × 10.sup.−5 0.0823 25 N.sub.2 9.925 × 10.sup.−5 −4.665 × 10.sup.−4 0.0943 (mPEG)ZIF-8 15 O.sub.2 1.188 × 10.sup.−4 −5.430 × 10.sup.−4 0.1129 25 O.sub.2 1.030 × 10.sup.−4 −4.675 × 10.sup.−4 0.0979 37 O.sub.2 8.352 × 10.sup.−5 −1.001 × 10.sup.−4 0.0793 25 N.sub.2 9.633 × 10.sup.−5 −7.348 × 10.sup.−4 0.0915 ZIF-67 25 O.sub.2 1.131 × 10.sup.−4 −7.942 × 10.sup.−4 0.1074 25 N.sub.2 1.032 × 10.sup.−4 −4.380 × 10.sup.−4 0.0980 ZSM-5 25 O.sub.2 1.685 × 10.sup.−4 0.00264 0.3116

TABLE-US-00006 TABLE 6 Summary of single site Langmuir-Freundlich fits to solid-state CO.sub.2 adsorption data at 25° C., where q.sub.sat is the saturation capacity (mmol/g), b is the Langmuir parameter (bar.sup.−v), v is the Freundlich parameter (dimensionless), P is pressure (bar), and n is the amount adsorbed [00015]$\left(\mathrm{mmol}/g\right)\mathrm{with}n=\frac{q_{\mathrm{sat}}{\mathrm{bP}}^v}{1+b{P}^v}.$ Material T (° C.) Gas q.sub.sat b v silicalite-1 25 CO.sub.2 3.382 1.026 1.020  (calcined) silicalite-1 (non- 25 CO.sub.2 9.408 4.263 × 10.sup.−5 0.7707 calcined) LTL 25 CO.sub.2 3.383 3.926 0.7682

TABLE-US-00007 TABLE 7 Henry's law constants for pure O.sub.2 and CO.sub.2 solubility in water used in this work. T Henry's constant Material (° C.) Gas (mmol/L .Math. mbar) Reference water 15 O.sub.2 0.00153 Error! Bookmark not defined. 25 O.sub.2 0.00127 Error! Bookmark not defined. 37 O.sub.2 0.00107 Error! Bookmark not defined. 25 CO.sub.2 0.03385 Error! Bookmark not defined.

TABLE-US-00008 TABLE 8 Comparison of adsorption capacity at 1 bar and 25° C. on a gravimetric basis for silicalite-1 and water. Adsorption capacity at 1 bar, 25° C. Material Gas (mmol/g) silicalite-1 O.sub.2 0.166 CO.sub.2 1.71 water O.sub.2 1.27 × 10.sup.−3 CO.sub.2 3.37 × 10.sup.−3

TABLE-US-00009 TABLE 9 Experimental and expected gas absorption values for pure-water control experiments. All values are an average of three separate doses at equivalent pressures. The difference between experimental and expected is within the accuracy of the measurement. Experimental Expected Standard T Pressure Solubility Solubility deviation Gas (° C.) (bar) (mmol/L) (mmol/L) (mmol/L) O.sub.2 25 419.5 −0.20 0.53 ±0.321 CO.sub.2 25 395.9 12.5 13.4 ±0.0416

TABLE-US-00010 TABLE 10 | Data recorded for three injections of oxygenated aqueous solutions of ZSM-5 nanocrystals (39.0 vol %) into deoxygenated water. Each injection was into a fresh vial of deoxygenated water, and the cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 13.5 1.282 0.39 18.11 206 76.0 2 18.0 1.282 0.46 20.16 186 73.6 3 16.0 1.282 0.34 17.92 170 69.1

TABLE-US-00011 TABLE 11 | Data recorded for three injections of oxygenated aqueous solutions of 90-nm silicalite-1 nanocrystals (12.5 vol %) into deoxygenated water. Each injection was done into a fresh vial of deoxygenated water, and the cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 14.0 1.282 0.77 11.60 95.0 92.8 2 24.0 1.282 0.57 14.54 78.1 80.8 3 17.0 1.282 0.84 13.32 94.4 92.2

TABLE-US-00012 TABLE 12 | Data recorded for three injections of oxygenated aqueous solutions of 90-nm silicalite-1 nanocrystals (3.6 vol %). Each injection was done into a fresh vial of deoxygenated water, and the cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 45 1.239 0.12 10.21 24.7 79.1 2 40 1.239 0.23 8.44 21.6 69.5 3 40 1.239 0.13 8.71 22.5 72.3

TABLE-US-00013 TABLE 13 | Data recorded for five injections of oxygenated aqueous solutions of (mPEG)ZIF-8 nanocrystals (6.6 vol %). Injections 1 and 3 were done in fresh vials of deoxygenated water, while injection 2 was done in the same vial as injection 1, and injections 4 and 5 were done in the same vial as injection 3. The cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 60 1.196 0.41 11.49 19.6  100% 2 72.5 1.196 11.49 18.78 16.9 85.3% 3 35 1.189 0.62 7.74 19.8  102% 4 22.5 1.189 7.74 11.24 19.5 99.9% 5 32.5 1.189 11.24 15.06 17.9 90.4%

TABLE-US-00014 TABLE 14 | Data recorded for three injections of oxygenated aqueous solutions of BSA/ZIF-67 (3.6 vol %). Each injection was done into a fresh vial of deoxygenated water, and the cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 102.5 1.239 0.48 9.21 8.9 70.7 2 102.5 1.239 0.33 10.37 10.6 86.5 3 52.5 1.239 0.61 6.11 10.4 84.1

TABLE-US-00015 TABLE 15 | Data recorded for three injections of air-equilibrated PEG/ZIF-8 solutions (3.6 vol %). Injections 1 and 3 were done into fresh vials of deoxygenated water, while injection 2 was done into the same vial as injection 1. The cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above, with the initial cO.sub.2 of injection 2 taken as the final, post-correction cO.sub.2 of injection 1. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 100 1.154 0.08 0.87 0.9 5.0 2 100 1.154 0.87 1.59 0.9 4.8 3 100 1.174 0.21 1.06 1.3 10.0

TABLE-US-00016 TABLE 16 | Data recorded for three injections of air-equilibrated PEG/ZIF-67 (3.6 vol %) solutions. Injections 1 was done into a fresh vial of deoxygenated water, while injection 2 and 3 was done into the same vial as injection 1. The cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above, with the initial cO.sub.2 of injections 2 and 3 taken as the final, post-correction cO.sub.2 of injection 1 and 2, respectively. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 100 1.187 0.28 1.06 1.2 7.9 2 100 1.187 1.06 1.86 1.7 13.3 3 100 1.187 1.87 2.54 1.4 9.8

TABLE-US-00017 TABLE 17 | Data recorded for three injections of oxygenated aqueous solutions of zeolite LTL nanocrystals (4.8 vol %) equilibrated at 1 bar O.sub.2. Each injection was done into a fresh vial, and the cO.sub.2 final values were corrected for differences in measurement and calibration temperature as described above. Injected Vial cO.sub.2 cO.sub.2 O.sub.2 carrying % of volume volume initial final capacity theoretical Trial (μL) (mL) (mg/L) (mg/L) (mL/dL) capacity 1 155 1.181 0.17 5.36 2.7 −5.7 2 155 1.154 0.64 6.26 2.9 −1.4 3 150 1.181 0.61 5.57 2.7 −5.5

TABLE-US-00018 TABLE 18 Data recorded for three control injections of nitrogenated aqueous solutions of ZSM-5 (36 vol %). Each injection was done into a fresh vial of deoxygenated water, and negligible changes in the initial and final O.sub.2 concentrations were observed. Note that temperature corrections were not applied to the initial and final cO.sub.2 values. Injected Vial cO.sub.2 cO.sub.2 volume volume initial final Trial (PL) (mL) (mg/L) (mg/L) 1 19.0 1.282 1.24 1.18 2 14.0 1.190 0.88 1.00 3 17.0 1.282 0.86 0.85

TABLE-US-00019 TABLE 19 | Summary of ABG results following injection of various volumes of oxygenated aqueous solutions of 90-nm silicalite-1 nanocrystals (10.8 vol %). BL-1 corresponds to the baseline (pre-injection) values for the blood before each of the 50, 100, and 150 μL injections, while BL-2 corresponds to the baseline values for the blood before each of the 200 μL injections. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 7.177 38.9 <30.1 6.8  7.8% 86.8% BL-2 0 7.149 39.4 <30.1 7.2  8.6% 85.7% 1 50 7.088 42.1 <30.1 6.6 29.1% 65.6% 2 50 7.084 43.1 <30.1 6.8 27.2% 67.7% 3 50 7.088 42.4 <30.1 6.8 27.0% 67.9% 4 100 7.082 40.6 <30.1 6.5 45.3% 49.3% 5 100 7.080 41.1 <30.1 6.6 43.2% 51.3% 6 100 7.079 41.1 <30.1 6.6 43.7% 50.8% 7 150 7.069 40.4 <30.1 6.4 56.5% 38.2% 8 150 7.064 39.7 <30.1 6.4 68.0% 26.7% 9 150 7.065 39.8 <30.1 6.4 67.0% 27.8% 10 200 7.068 39.2 31.3 6.5 74.4% 20.6% 11 200 7.066 39.1 35.2 6.5 79.1% 16.0% 12 200 7.066 39.1 33.6 6.5 77.3% 17.7%

TABLE-US-00020 TABLE 20 | Summary of ABG results following injection of various volumes of nitrogenated aqueous solutions of 90-nm silicalite-1 nanocrystals (10.8 vol %). BL-1,2 corresponds to the baseline (pre-injection) values for trials 1 and 2, while BL-3-9 corresponds to the baseline for trials 3 through 9. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1,2 0 7.481 38.5 132 6.9  7.7% 90.9% BL-3-9 0 7.352 38.5 <30.1 7.1  9.1% 89.5% 1 50 7.342 38.5 <30.1 6.9 10.2% 88.1% 2 50 7.342 38.4 <30.1 6.9 11.0% 87.1% 3 50 7.344 37.5 <30.1 6.9 11.3% 86.9% 4 100 7.351 35.7 <30.1 7.0  9.9% 88.4% 5 100 7.348 35.6 <30.1 6.6 12.0% 86.1% 6 100 7.348 35.7 <30.1 6.6 12.6% 85.6% 7 150 7.344 34.7 <30.1 7.0 12.3% 85.8% 8 150 7.341 34.8 <30.1 7.4 11.3% 86.9% 9 150 7.341 34.9 <30.1 7.5 12.1% 86.1%

TABLE-US-00021 TABLE 21 | Summary of ABG results following injection of various volumes of oxygenated aqueous solutions of 60-nm silicalite-1 nanocrystals (9.1 vol %). BL-1, BL-2, and BL-3 correspond to the baseline (pre-injection) values for the blood before the 50, 100, and 150 μL injections, respectively. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 7.097 41.3 <30.1 6.4    6.1% 88.9% BL-2 0 7.09 42.8 <30.1 6.5    4.9% 90.1% BL-3 0 7.093 41.8 <30.1 6.3  <3.3% 93.4% 1 50 7.065 41.8 <30.1 6.4   24.0% 71.0% 2 50 7.069 41.9 <30.1 6.4   23.2% 72.1% 3 50 7.066 41.9 <30.1 6.4   27.5% 67.6% 4 100 7.038 43.1 <30.1 6.2   40.8% 54.4% 5 100 7.046 42.9 <30.1 6.3   31.8% 63.5% 6 100 7.045 41.4 <30.1 6.4   45.7% 49.5% 7 150 7.016 41.9 <30.1 6.0   52.3% 43.3% 8 150 7.025 42.2 <30.1 5.9   47.6% 47.9% 9 150 7.009 41.9 <30.1 5.8   56.9% 38.8%

TABLE-US-00022 TABLE 22 | Summary of ABG results following injection of various volumes of oxygenated aqueous solutions of (mPEG)ZIF-8 nanocrystals (6.6 vol %). BL-1 corresponds to the baseline (pre-injection) values for the blood before each of the 50, 100, and 150 μL injections. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 6.978 39.9 <30.1 3.8 12.6% 84.7% 1 50 7.703 <15.4 <30.1 3.7 25.9% 70.6% 2 50 7.723 <15.4 <30.1 3.7 27.6% 69.3% 3 50 7.736 <15.4 <30.1 3.7 26.6% 69.8% 4 100 7.664 <15.4 <30.1 3.6 34.1% 61.8% 5 100 7.698 <15.4 <30.1 3.5 36.6% 59.3% 6 100 7.636 <15.4 <30.1 3.6 35.0% 60.9% 7 150 7.726 <15.4 <30.1 3.5 47.1% 48.2% 8 150 7.712 <15.4 <30.1 3.5 45.1% 50.6% 9 150 7.697 <15.4 <30.1 3.5 42.1% 53.6%

TABLE-US-00023 TABLE 23 | Summary of ABG results following injection of various volumes of nitrogenated aqueous solutions of (mPEG)ZIF-8 nanocrystals (6.6 vol %). BL-1 corresponds to the baseline (pre-injection) values for the blood before each of the 50, 100, and 150 μL injections. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 6.944 39.4 <30.1 4.2 11.0% 87.2% 1 50 7.631 <15.4 <30.1 4.0 13.9% 83.6% 2 50 7.694 <15.4 <30.1 4.1 12.2% 85.9% 3 50 7.716 <15.4 <30.1 4.1 12.5% 85.3% 4 100 7.698 <15.4 <30.1 4.0 20.8% 76.7% 5 100 7.704 <15.4 <30.1 4.1 17.3% 80.2% 6 100 7.716 <15.4 <30.1 4.1 15.1% 82.7% 7 150 7.645 <15.4 <30.1 3.9 20.2% 76.7% 8 150 7.67 <15.4 <30.1 3.9 13.3% 84.5% 9 150 7.673 <15.4 <30.1 3.8 16.6% 80.8%

TABLE-US-00024 TABLE 24 | Summary of ABG results following injection of various volumes of nitrogenated aqueous solutions of the highest concentration of silicalite-1 dispersion tested. BL-1 corresponds to the baseline (pre-injection) values for the blood before each of the 25 and 50 μL injections. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 7.387 40.8 <30.1 7.8  8.90% 89.50% 1 25 7.347 42 <30.1 7.9 24.50% 73.60% 2 25 7.328 44.4 <30.1 8.0 21.70% 76.40% 3 25 7.33 43.6 <30.1 8.1 21.80% 76.60% 4 50 7.382 37.8 <30.1 7.8 42.10% 56.90% 5 50 7.337 42.9 <30.1 8.0 31.00% 67.10% 6 50 7.349 40.6 <30.1 7.6 34.50% 63.60%

TABLE-US-00025 TABLE 25 | Summary of ABG results following injection of various volumes of an oxygenated aqueous solution of 5% (w/v) dextrose. BL-1 corresponds to the baseline (pre-injection) values for the blood before each of the 50, 100, and 150 μL injections. A value that is below the detection limit for that parameter on the ABG is denoted by a < followed by the upper bound of that value. Injection pCO.sub.2 pO.sub.2 ctHb Trial vol (μL) pH (mmHg) (mmHg) (g/dL) FO.sub.2Hb FHHb BL-1 0 7.334 38.6 <30.1 7.1  3.8% 95.1% 1 50 7.323 38.1 <30.1 6.8 11.0% 88.1% 2 50 7.327 38 <30.1 6.8  8.5% 90.3% 3 50 7.332 37.3 <30.1 6.9 10.0% 89.0% 4 100 7.33 36.5 <30.1 6.7  8.9% 90.0% 5 100 7.328 36.6 <30.1 6.6 11.6% 87.5% 6 100 7.326 37 <30.1 6.7 10.4% 88.7% 7 150 7.323 36.3 <30.1 6.5 11.6% 87.2% 8 150 7.318 36.8 <30.1 6.5 12.3% 86.5% 9 150 7.323 36.1 <30.1 6.5 13.1% 85.8%

TABLE-US-00026 TABLE 26 Summary of the O.sub.2 carrying capacities obtained for each aqueous solution from the amount of O.sub.2 released to deoxygenated blood as a function of injection volume. O.sub.2 carrying capacity Sample (mL/dL) 90 nm silicalite-1 (high-concentration) 110 90 nm silicalite-1 (10.8 vol %) 59.1 ± 2.7  60 nm silicalite-1 (9.1 vol %) 50.5 ± 1.3  (mPEG)ZIF-8 (6.6 vol %) 16.2 ± 1.4  5% dextrose 4.0 ± 1.4

TABLE-US-00027 TABLE 37 Calculation of the estimated pO.sub.2 for three injections of 200 μL of oxygenated aqueous solutions of 90-nm silicalite-1 nanocrystals and comparison with the experimental pO.sub.2 reported. Errors between calculated and experimental values are given in parentheses. All pressures are in mmHg. (pO.sub.2).sub.c Trial pO.sub.2 SO.sub.2 Severinghaus 1 31.3 78.30% 30.9 (1.23%) 2 35.2 83.20% 34.9 (0.80%) 3 33.6 81.40% 33.3 (0.83%)

[0111] Other embodiments are in the claims.