Macrocycle Embedded Organic Electronic Materials, Composites, and Compositions for Chemical Sensing

Abstract

A semiconductor sensor device for detecting an analyte including a semiconducting layer, one or more organic molecules in the semiconducting layer, and one or more receptor molecules, comprising a poly-cyanostilbene macrocycle, wherein the one or more receptors is embedded within or onto the semiconducting layer of the semiconductor sensor device. Also disclosed is a method of preparing the semiconductor sensor device including a step of coupling the one or more receptor molecules into or onto the semiconducting layer of the semiconductor sensor device, a dielectric surface, or an electrode surface. Also described is chemical sensing device including the semiconductor sensor device and other elements of a sensing device.

Claims

1. A semiconductor sensor device for detecting an analyte, comprising a semiconducting layer, one or more organic molecules in the semiconducting layer, and one or more receptor molecules, comprising a poly-cyanostilbene macrocycle according to Formula I: ##STR00009## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH3, hydrogen, enthynyl, arylethynylene, -halo, —OR.sup.9, —N(R.sup.10R.sup.11), —CO.sub.2R.sup.12, —C(O)—N(R.sup.13R.sup.14), wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each independently selected from the group consist of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, hydrogen, wherein the one or more receptor molecules are embedded within or onto the semiconducting layer of the semiconductor sensor device.

2. The device of claim 1, wherein the one or more organic molecules are small molecules having a number average molecule weight of from about 50 g/mol to about 5,000 g/mol, as measured by gel permeation chromatography and/or NMR.

3. The device of claim 1, wherein the one or more organic molecules are polymer comprising repeat units (n) ≥15, and having a molecular weight from about 15,000 g/mol to about 500,000 g/mol, as measured by gel permeation chromatography.

4. The device of claim 1, having a loading percentage of the one or more organic molecules to the one or more receptor molecules of from about 1 to about 50 wt. %

5. The device of claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each a tert-butyl group.

6. The device of claim 1, wherein the one or more organic molecules comprises poly[[2,5-bis(2-decyltetradecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl][2,2′-bithiophene]-5,5′-diyl-(1E)-1,2-ethenediyl[2,2′-bithiophene]-5,5′-diyl] (PDVT)

7. The device of claim 1, wherein the one or more organic molecules comprises a conjugated polymer according to Formula (II): ##STR00010## wherein E represents an “electron donating group”, R.sup.6 and R.sup.7 are each independently selected from a hydrocarbyl group comprising from 1 to about 50 carbon atoms, R.sup.8 may be a hydrocarbyl group comprising from 1 to about 20 carbon atoms, or a thiophene group, and n may be an integer of greater than 15.

8. The device of claim 1, further comprising a two-terminal chemresistor, comprising a source electrode and a drain electrode with a chemically sensitive semiconductor material comprising a channel.

9. The device of claim 1, further comprising a three-terminal transistor, comprising a source, a drain, and a gate electrode, configured to enhance the electrical conductivity of a chemically sensitive semiconductor material.

10. A method of preparing the semiconductor sensor device of claim 1, comprising a step of coupling the one or more receptor molecules into or onto the semiconducting layer of the semiconductor sensor device, a dielectric surface, or an electrode surface.

11. The method of claim 10, wherein the one or more organic molecules and the one or more receptor molecules are deposited via spin-coating, drop-casting, dip-coating, slot-die coating, doctor blading, or bar coating to form one or more semiconducting layers.

12. The method of claim 10, wherein the one or more organic molecules and the one or more receptor molecules are within a same layer of the device.

13. The method of claim 10, wherein the one or more organic molecules and the one or more receptor molecules are in different layers of the device.

14. The method of claim 10, wherein the one or more receptors are chemically incorporated into the one or more organic molecules via chemical reaction throughout a same layer of the device.

15. The method of claim 10, wherein the one or more receptor molecules are physically entrapped in the semiconducting layer.

16. A chemical sensor system for detecting analyte comprising a semiconductor sensor device comprising one or more transistors, and each of the one or more transistors comprises a conductive channel, and the conductive channel comprises a semiconducting layer comprising one or more organic molecules, and one or more receptor molecules, comprising a poly-cyanostilbene macrocycle according to Formula (I): ##STR00011## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, hydrogen, enthynyl, arylethynylene, -halo, —OR.sup.9, —N(R.sup.10R.sup.11), —CO.sub.2R.sup.12, —C(O)—N(R.sup.13R.sup.14) wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each independently selected from the group consist of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, hydrogen, wherein the one or more receptors is embedded within or onto the semiconducting film of the semiconductor sensor device, a sample configured to hold a target molecule and the target molecule has a selective affinity to bind with the one or more receptor molecules, an assay system configured to bring the semiconductor sensor device in contact with the sample, a digital read-out, and a data processing system.

17. The system of claim 16, wherein the system comprises two or more semiconductor sensor devices.

18. The system of claim 16, wherein the system is configured to operate through the chemical doping of a semiconducting layer upon interaction with the analyte, wherein the semiconducting layer comprises the one or more receptor molecules.

19. The system of claim 16, wherein the system is configured to operate through the chemical dedoping of an active layer upon interaction with the analyte, wherein the active layer comprises the one or more receptor molecules.

20. The system of claim 16, wherein the system is configured to detect a single analyte.

21. The system of claim 16, wherein the system is configured to detect multiple analytes of different chemical identifies and classifications.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0040] The drawings, which are incorporated in and form a portion of the specification, illustrate certain embodiments of the invention and, together with the entire specification, are meant to explain these embodiments of the present invention to those skilled in the art. The drawings supplement the specification and are intended to illustrate further the invention and its advantages. The figures and drawings shown or described in this disclosure and in the Detailed Description of the Invention are as follows:

[0041] FIG. 1 shows a representation of the OFET device architecture utilized in the present invention.

[0042] FIG. 2 shows the chemical structures of the OFET semiconducting layer constituents: poly[[2,5-bis(2-decyltetradecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl][2,2′-bithiophene]-5,5′-diyl-(1E)-1,2-ethenediyl[2,2′-bithiophene]-5,5′-diyl] (PDVT) conjugated polymer and poly-cyanostilbene macrocycle, cyanostar (CS), receptors.

[0043] FIG. 3 shows a graphical representation of the current-voltage (I-V) scans of PDVT and PDVT:CS blend films, wherein the horizontal axis represents applied voltage, and the vertical axis represents the electrical current response. Chemical doping trends with a concomitant increase in electrical current response as a function of CS loading within the PDVT host matrix.

[0044] FIG. 4 shows a graphical representation of PDVT:CS blend films, wherein the vertical axes represent conductivity and field-effect mobility.

[0045] FIG. 5 shows the Kelvin probe force microscopy (KPFM) on the PDVT and PDVT-CS (20 wt %) films deposited on indium tin oxide (ITO) glass substrates. Measurements were performed by scanning over the polymer/ITO border. The surface potential profile between the two films is shown. A drop-off in the potential profile indicates there is a transformation in the surface energetics.

[0046] FIG. 6 shows a representation of semiconducting layer constituents PDVT, CS, and tetrabutylammonium (TBA-X, X=dihydrogen phosphate (P), nitrate (N), chloride (Cl), hydrogen sulfate (HS), and perchlorate(PC)) organic salts to study anion-induced electronic perturbations in back-gate transistor architectures.

[0047] FIG. 7 shows a graphical representation of 2-point probe I-V measurements, wherein the horizontal axis represents applied voltage, and the vertical axis represents the change in current (amperes). The observed reduction in bulk current was found to be attributed to CS-anion host-guest complexation.

[0048] FIG. 8A shows a graphical representation of a back-gate OFET transfer characteristics of PDVT-CS and PDVT-CS⋅TBA-X films, wherein the horizontal axis represents gate-source voltage (V.sub.GS), and the vertical axis represents drain-source current (I.sub.DS) at a constant drain-source voltage (V.sub.DS) of −60 V.

[0049] FIG. 8B shows a graphical representation of the transfer characteristics of PDVT-CS and PDVT-CS⋅TBA-X films, wherein the horizontal axis represents V.sub.GS, and the vertical axis represents √{square root over (I.sub.DS)}.

[0050] FIG. 9 shows an interval plot representing changes to the carrier concentration for PDVT, PDVT-CS, and PDVT-CS⋅TBA-X films.

[0051] FIG. 10 shows an interval plot representing changes to the bulk conductivity for PDVT, PDVT-CS, and PDVT-CS⋅TBA-X films.

[0052] FIG. 11 shows an interval plot representing changes to the OFET on/off ratio for PDVT, PDVT-CS, and PDVT-CS⋅TBA-X films.

[0053] FIG. 12 shows an interval plot representing changes to the OFET mobility for PDVT, PDVT-CS, and PDVT-CS⋅TBA-X films.

[0054] FIG. 13A is an illustration of the receptor's reversible binding. CS-anion complexation and anion removal before and after submersion in deionized (DI) water for 1 hr, respectively

[0055] FIG. 13B shows the OFET mobility of CS-anion complexation and anion removal before and after submerging the films in water, respectively.

[0056] FIG. 13C shows the bulk conductivity of CS-anion complexation and anion removal before and after submerging the films in water, respectively.

[0057] FIG. 13D shows the OFET on/off ratio of CS-anion complexation and anion removal before and after submerging the films in water, respectively.

[0058] FIG. 13E shows the carrier concentration of CS-anion complexation and anion removal before and after submerging the films in water, respectively.

[0059] FIG. 14 shows the storage stability of PDVT-CS exposed to N.sub.2 (dark) over a 60-day period.

[0060] FIG. 15 shows the storage stability of PDVT-CS exposed to air (dark) over a 60-day period.

[0061] FIG. 16 shows the storage stability of PDVT-CS exposed to ultrapure (UP, Type 1) DI water (dark) over a 60-day period.

[0062] FIG. 17 shows the storage stability of PDVT-CS exposed to Instant Ocean® sea salt electrolyte (dark) over a 60-day period.

[0063] FIG. 18 shows a representation of the PDVT-CS EGOFET device architecture utilized in the present invention.

[0064] FIG. 19 shows an EGOFET HEPES buffer (baseline solution) transient responses at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V.

[0065] FIG. 20A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards dihydrogen phosphate (H.sub.2PO.sub.4.sup.−) in HEPES solution.

[0066] FIG. 20B shows PDVT-CS EGOFET calibration plot towards H.sub.2PO.sub.4.sup.− in HEPES solution.

[0067] FIG. 21A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards nitrate (NO.sub.3.sup.−) in HEPES solution.

[0068] FIG. 21B shows PDVT-CS EGOFET calibration plot towards NO.sub.3.sup.− in HEPES solution.

[0069] FIG. 22A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards metasilicate (SiO.sub.3.sup.2−) in HEPES solution.

[0070] FIG. 22B shows PDVT-CS EGOFET calibration plot towards SiO.sub.3.sup.2− in HEPES solution.

[0071] FIG. 23A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards bromide (Br.sup.−) in HEPES solution.

[0072] FIG. 23B shows PDVT-CS EGOFET calibration plot towards Br.sup.− in HEPES solution.

[0073] FIG. 24A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards bicarbonate (HCO.sub.3.sup.−) in HEPES solution.

[0074] FIG. 24B shows PDVT-CS EGOFET calibration plot towards HCO.sub.3.sup.− in HEPES solution.

[0075] FIG. 25A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards carbonate (CO.sub.3.sup.2−) in HEPES solution.

[0076] FIG. 25B shows PDVT-CS EGOFET calibration plot towards CO.sub.3.sup.2− in HEPES solution.

[0077] FIG. 26A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards sulfate (SO.sub.4.sup.2−) in HEPES solution.

[0078] FIG. 26B shows PDVT-CS EGOFET calibration plot towards SO.sub.4.sup.2− in HEPES solution.

[0079] FIG. 27A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards chloride (Cr.sup.−) in HEPES solution.

[0080] FIG. 27B shows PDVT-CS EGOFET calibration plot towards Cl.sup.− in HEPES solution.

[0081] FIG. 28A shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards H.sub.2PO.sub.4.sup.− in artificial seawater.

[0082] FIG. 28B shows PDVT-CS EGOFET a calibration plot towards H.sub.2PO.sub.4.sup.− in artificial seawater.

[0083] FIG. 29 shows PDVT-CS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards pH fluctuations (4, 7, and 10).

[0084] FIG. 30A shows PDVT-TBAP (without CS) transfer characteristics. These results show how the charge transport is affected by polymer-analyte interactions. In p-channel conduction mode the profiles show significant degradation.

[0085] FIG. 30B shows PDVT-TBAP (without CS) transfer characteristics, wherein the vertical axis represents √{square root over (I.sub.DS)}.

[0086] FIG. 30C shows PDVT-TBAN (without CS) transfer characteristics. These results show how the charge transport is affected by polymer-analyte interactions. In p-channel conduction mode the profiles show significant degradation.

[0087] FIG. 30D shows PDVT-TBAN (without CS) transfer characteristics, wherein the vertical axis represents √{square root over (I.sub.DS)}.

[0088] FIG. 31A shows the UV-Vis absorption spectra of CS undergoing photoisomerization in CHCl.sub.3 solutions.

[0089] FIG. 31B illustrates the anion recognition properties of CS with the binding affinity altered by macrocycle conformation.

[0090] FIG. 32A shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards H.sub.2PO.sub.4.sup.− in HEPES solution.

[0091] FIG. 32B shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards NO.sub.3.sup.− in HEPES solution.

[0092] FIG. 32C shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards SiO.sub.3.sup.2− in HEPES solution.

[0093] FIG. 32D shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards Br.sup.− in HEPES solution.

[0094] FIG. 32E shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards HCO.sub.3.sup.− in HEPES solution.

[0095] FIG. 32F shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards CO.sub.3.sup.2− in HEPES solution.

[0096] FIG. 32G shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards SO.sub.4.sup.2− in HEPES solution.

[0097] FIG. 32H shows PDVT-isoCS EGOFET transient responses (at V.sub.GS=−0.7 V and V.sub.DS=−1.0 V) towards Cl.sup.− in HEPES solution.

DETAILED DESCRIPTION OF INVENTION

[0098] The present invention provides novel soft matter electronic devices that are prepared using straightforward processing methods resulting in highly sensitive, selective, and reproducible sensors for anions. Furthermore, this invention provides alternative methods utilizing organic semiconductors and macrocyclic molecules with tunable electrical properties for targeted sensing applications. The invention demonstrates a novel composite film transistor-based platform, that provides high selectivity and sensitivity in complex environments and in the presence of interfering ions.

[0099] The present invention provides several advantages when compared to traditional and contemporary sensing approaches involving both soft matter and inorganic materials systems. These include: 1) a method that overcomes challenges associated with OFET fabrication practices involving the use of 2-D materials, molecularly imprinted polymer (MIP) matrices, nanoparticles, aptamers, enzymes, and other biomacromolecules; 2) high sensitivity towards weakly coordinating anions; 3) sensors operating in deionized (DI) water and complex aqueous media; 4) a methodology that allows for the discrimination of analytes based on multifaceted analyte characteristics (molecule size, shape, and charge). The above advantages coupled with the synthetic tunability of organic semiconductors and macrocyclic receptor chemistries enables access to unique optoelectronic and sensing properties, providing significant potential for advancing anion sensing technologies, including but not limited to environmental and point-of-care medical diagnostics.

[0100] In one aspect, the present disclosure relates to a semiconductor sensor device for the detection of anionic molecules. The device includes a semiconductor layer comprising one or more films, comprising one or more organic molecules, and one or more receptor molecules (probe), comprising a poly-cyanostilbene macrocycle according to Formula I:

##STR00004##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently selected from the group consisting of a hydrocarbyl group comprising from 1 to 30 carbon atoms or from about 2 to 20 carbon atoms or from about 2 to 10 carbon atoms, an alkenyl group comprising from 2 to 30 carbon atoms, or from about 2 to 20 carbon atoms, or from about 2 to 10 carbon atoms, an alkyl group comprising from 2 to 30 carbon atoms, or from about 2 to 20 carbon atoms, or from about 2 to 10 carbon atoms, an alkoxy group comprising from 1 to 30 carbon atoms, or from about 1 to 20 carbon atoms, or from about 1 to 10 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, or from about 6 to 12 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, ethynyl, arylethynylene, hydrogen, -halo, —OR.sup.9, —N(R.sup.10R.sup.11) , —CO.sub.2R.sup.12, —C(O)—N(R.sup.13R.sup.14), wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, an aryl group comprising from 6 to 20 carbon atoms, an arylalkyl group comprising from 7 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, and hydrogen, wherein the one or more receptors is embedded within or onto the semiconducting layer.

[0101] The one or more organic molecules of the semiconductor sensor device may be small molecules, having a molecular weight of from about 50 g/mol to about 5,000 g/mol, as measured by gel permeation chromatography and NMR. Suitable examples of small organic molecules may be tetracene, pentacene, naphthalene diimide, and phthalocyanine.

[0102] The one or more organic molecules of the semiconductor sensor device may be oligomers having repeating units (n) of integer values between about 2 and 14, and a molecular weight of from about 300 g/mol to about 10,000 g/mol. Suitable examples of oligomer organic molecules may be selected from 1H-pyyrole, 3-4-ethylenedioxythiophene, 9H-fluorene, and p-phenylene.

[0103] The one or more organic molecules of the semiconductor sensor device may be polymers with repeating units (n) of integer values ≥15, or greater than 20, or greater than 30 or greater than 50, and a molecular weight from about 15,000 g/mol to about 500,000 g/mol.

[0104] For example, the one or more organic molecules may include a conjugated polymer according to Formula (II):

##STR00005##

wherein E represents an “electron donating group”, R.sup.6 and R.sup.7 are each independently selected from a hydrocarbyl group comprising from 1 to about 50 carbon atoms, or from about 1 to 30 carbon atoms, R.sup.8 may be a hydrocarbyl group comprising from 1 to about 20 carbon atoms, or a thiophene group, and n may be an integer of greater than 15.

[0105] The term “electron donating group” refers to a group that has the net effect of increasing electron density in a molecule through a carbon atom it is bonded to via inductive or resonance effects. Exemplary electron donating groups include thiophene groups (C.sub.4H.sub.4S), ether groups (e.g., —O—), hydroxyl groups (e.g., —OH), amine groups (e.g., —NH.sub.2, —NR.sup.9, etc.), arene groups (e.g., phenyl), and C.sub.1-C.sub.20 hydrocarbyl groups (e.g. —CH.sub.3), wherein R.sup.9 may be a hydrocarbyl group comprising from 1 to 20 carbon atoms. For example, the electron donating group may comprise of one or more thiophene groups, or two or more thiophene groups, or three or more thiophene groups, or a polythiophene according to the following structure:

##STR00006##

[0106] Suitable examples of polymeric organic molecules may include poly[[2,5-bis(2-decyltetradecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl][2,2′-bithiophene]-5,5′-diyl-(1 E)-1,2-ethenediyl[2,2′-bithiophene]-5,5′-diyl] (PDVT), poly [2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPP-DTT), poly[2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione -3,6-diyl)-alt-(2,2′;5′,2″;5″,2′″-quaterthiophen-5,5′″-diyl)] (DPP-4T), poly(3-hexylthiophene-2,5-diyl) (P3HT), and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS).

[0107] The one or more organic molecules may be reticular chemistries, having small organic molecules connected by linkages consisting of boroxine, imine, hydrazone, azine, and ketoenamine.

[0108] The two or more organic molecules may be the same or different. Sometimes, two or more organic molecules are the same. Sometimes, the two or more organic molecules are different.

[0109] The one or more receptors (probes) may be a poly-cyanostilbene macrocycle, called cyanostar, according to the Formula (I):

##STR00007##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 30 carbon atoms, or from about 2 to 20 carbon atoms, or from about 2 to 10 carbon atoms, an alkyl group comprising from 2 to 30 carbon atoms, or from about 2 to 20 carbon atoms, or from about 2 to 10 carbon atoms, alkoxy group comprising from 1 to 30 carbon atoms, or from about 1 to 20 carbon atoms, or from about 1 to 10 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, or from about 6 to 12 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, ethynyl, arylethynylene, hydrogen, -halo, —OR.sup.9, −N(R.sup.10R.sup.11), —CO.sub.2R.sup.12, —C(O)—N(R.sup.13R.sup.14), wherein R.sub.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each independently selected from the group consisting of alkenyl group comprising from 2 to 20 carbon atoms, alkyl group comprising from 2 to 20 carbon atoms, alkoxy group comprising from 2 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, aryl group comprising from 6 to 20 carbon atoms, arylalkyl group comprising from 7 to 20 carbon atoms, cycloalkyl group comprising from 4 to about 20 carbon atoms, heteroaryl group comprising from 5 to 20 carbon atoms, heterocycle group comprising from 3 to about 20 carbon atoms, haloalkyl group comprising from 1 to 20 carbon atoms, and hydrogen. R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 may each be a tert-butyl substituent group.

[0110] The one or more receptors may be any shape-persistent macrocycle. The one or more receptor molecules may include two or more receptor molecules, wherein the two or more receptor molecules are the same or different. Sometimes, the two or more receptor molecules are the same. Sometimes, the two or more receptor molecules are different

[0111] The device of the foregoing embodiments may include a two-terminal chemiresistor including a source and a drain electrode with a chemically sensitive semiconductor material comprising a channel. The device may operate through a change in electrical resistance of the semiconductor material interacting with a target molecule. Devices may include variable channel lengths and channel widths with either linear or interdigitated electrode patterns, wherein the length ranges from 1 μm-10 mm and the width ranges from 100 μm-50 mm.

[0112] The device of the foregoing embodiments may include a three-terminal transistor including a source, a drain, and an insulated gate electrode configured to enhance the electrical conductivity of a chemically sensitive semiconductor material, resulting in greater signal amplification in response to an interacting or absorbed target molecule. The devices can include variable channel lengths and channel widths with either linear or interdigitated electrode patterns. The devices can include top-gate, bottom-gate, and extended-gate configurations. The devices can operate in either accumulation or depletion mode.

[0113] The device of the foregoing embodiments may include of a three-terminal transistor including a source and drain electrode in conjunction with a gate electrode and a chemically sensitive semiconductor material in direct contact with an electrolyte. The gate voltage can be controlled through the contributions of a reference and counter electrode while the source and drain voltage can be applied via an external source-meter unit. The devices can include variable channel lengths and channel widths with either linear or interdigitated electrode patterns. The devices can operate in either accumulation or depletion mode.

[0114] The device of the foregoing embodiments may include a collinear four-terminal device configurations to measure the change in electrical resistance in response to an interacting or absorbed target molecule.

[0115] In a second aspect, the present disclosure relates to a method for fabricating the foregoing embodiments of the semiconductor sensor device for the detection of anionic molecules. Various solution-processing methods may be employed to create layers which are comprised of a mixture or layers of semiconducting materials and the one or more organic molecules between two or more collinear electrodes and in proximity to one or more gate electrodes. The fabrication protocol includes the coupling of one or more receptor molecules into or onto the semiconducting layer, dielectric surface, or electrode surface, wherein the dielectric surface corresponds to the floor of the semiconductor sensor device, near the back gate, as depicted in FIG. 1.

[0116] The semiconductor sensor device may be fabricated such that the one or more receptor molecules and the one or more organic molecules are within the same layer of the device. The device may also be fabricated such that the one or more receptor molecules and the one or more organic molecules are in different layers of the device.

[0117] The one or more receptor molecules of the foregoing embodiments may be chemically incorporated into the organic molecule(s) via chemical reaction throughout the same layer or the one or more receptor molecules may be chemically incorporated onto the surface of a separate layer containing the one or more organic molecules, or the one or more receptor molecules may be chemically incorporated onto the surface of a dielectric surface via chemical reaction throughout the same layer or by establishment of well-ordered films via physical vapor deposition, or the one or more receptor molecules may be chemically incorporated onto the surface of an electrode via chemical reaction throughout the same layer.

[0118] In each of the foregoing embodiments, the one or more receptor molecules may be physically entrapped in the organic film formed by the one or more organic molecules.

[0119] The semiconductor sensor device may have layers ranging from a monolayer to a thickness of <500 nm, or a thickness of >500 nm to <10 μm, as measured by profilometry or atomic force microscopy (AFM).

[0120] The one or more receptors and the one or more organic molecules may form the semiconducting layer of the sensor device which may be deposited via spin-coating, drop-casting, dip-coating, slot-die coating, doctor blading, and bar coating. The semiconducting layers may be optimized via post-deposition techniques such as solvent-vapor, thermal annealing, and crosslinking.

[0121] In a third aspect, the present disclosure relates to a chemical sensor system for the detection of anions in real-world samples (medical, environmental, high ionic strength, aqueous, threat, etc.). The sensor system at least comprises a sensor device, a sample, an assay system, a digital read-out, and a data processing system. The sensor device includes one or more transistors, each of the transistors including a conductive channel. The channel comprises a semiconducting film comprising one or more organic molecules and one or more receptor molecules, comprising a poly-cyanostilbene macrocycle according to Formula (I):

##STR00008##

wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently selected from the group consisting of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclyl group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, hydrogen, enthynyl, arylethynylene, halo, OR.sup.9, —N(R.sup.10R.sup.11), —CO.sub.2R.sup.12, —C(O)—N(R.sup.13R.sup.14), wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each independently selected from the group consist of an alkenyl group comprising from 2 to 20 carbon atoms, an alkyl group comprising from 2 to 20 carbon atoms, an alkoxy group comprising from 2 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, a cycloalkyl group comprising from 4 to about 20 carbon atoms, a heteroaryl group comprising from 5 to 20 carbon atoms, a heterocyclic group comprising from 3 to about 20 carbon atoms, a haloalkyl group comprising from 1 to 20 carbon atoms, —(CH.sub.2).sub.1-20—NH—(CH.sub.2).sub.1-20—CH.sub.3, hydrogen,

[0122] The sample is capable of holding a target molecule that is configured to bind with one or more of the probe molecules (receptors). The assay system is configured to bring the sensor device in contact with the sample.

[0123] The one or more receptor molecules and one or more organic molecules enhances the electronic properties of the semiconductor. The semiconducting device of the chemical sensor system operates via chemical doping of the semiconducting layer upon interaction with the analyte or via chemical dedoping of the semiconducting layer upon interaction with the analyte.

[0124] The chemical sensor system of the foregoing embodiments may detect a single analyte, or the system is capable of detecting multiple analytes of different chemical identities and classifications.

[0125] The chemical sensor system of the foregoing embodiments may comprise of one or more semiconductor devices, or two or more semiconductor devices, or three or more semiconductor devices, or a plurality of semiconductor devices.

[0126] The chemical sensor system of the foregoing embodiments may be exposed to water-based media for measuring one or multiple chemical properties. Suitable examples of the water-based media may be environmental water with varying levels of salinity, nutrients, pollutants, biological components, and any other living or nonliving species. The water-based media may include biological water originating from living organisms with varying levels of salinity, nutrients, pollutants, biological components, and any other living or nonliving species.

[0127] The chemical sensor system of the foregoing embodiments may further include a microfluidic system which may be coupled to the one or more semiconducting device(s), wherein the chemical sensor system is capable of electrically isolating said semiconducting layer components from remaining components of said devices.

[0128] The chemical sensor system of the foregoing embodiments may include a microfluidic network which is configured to direct multiple samples to individual devices for parallel analysis.

[0129] All patents and publications cited herein are fully incorporated by reference herein in their entirety or at least for the portion of their description for which they are specifically cited or relied upon in the present description.

[0130] The patentees do not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.

[0131] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.

[0132] It is also to be understood that each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein is to be interpreted as also being disclosed in combination with each amount/value or range of amounts/values disclosed for any other component(s), compounds(s), substituent(s) or parameter(s) disclosed herein and that any combination of amounts/values or ranges of amounts/values for two or more component(s), compounds(s), substituent(s) or parameters disclosed herein are thus also disclosed in combination with each other for the purposes of this description.

[0133] It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, a range of from 1-4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4.

[0134] It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent, or parameter. Thus, this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range.

[0135] Furthermore, specific amounts/values of a component, compound, substituent or parameter disclosed in the description or an example is to be interpreted as a disclosure of either a lower or an upper limit of a range and thus can be combined with any other lower or upper limit of a range or specific amount/value for the same component, compound, substituent or parameter disclosed elsewhere in the application to form a range for that component, compound, substituent or parameter.

REFERENCES

[0136] The following references may be useful in understanding some of the principles discussed herein:

1. Inganas, O. , Organic Photovoltaics over Three Decades. Adv. Mater. 2018, 30 (35), e1800388.
2. Zheng, H.; Zheng, Y.; Liu, N.; Ai, N.; Wang, Q.; Wu, S.; Zhou, J.; Hu, D.; Yu, S.; Han, S.; Xu, W.; Luo, C.; Meng, Y.; Jiang, Z.; Chen, Y.; Li, D.; Huang, F.; Wang, J.; Peng, J.; Cao, Y., All-solution processed polymer light-emitting diode displays. Nat. Commun. 2013, 4, 1971.
3. Lee, Y. H.; Jang, M.; Lee, M. Y.; Kweon, O. Y.; Oh, J. H., Flexible Field-Effect Transistor-Type Sensors Based on Conjugated Molecules. Chem. 2017, 3, 724-763.
4. Irimia-Vladu, M., “Green” electronics: biodegradable and biocompatible materials and devices for sustainable future. Chem. Soc. Rev. 2014, 43, 588-610.
5. Lin, P.; Yan, F., Organic Thin-Film Transistors for Chemical and Biological Sensing. Adv. Mater. 2012, 24, 34.
6. Elkington, D.; Cooling, N.; Belcher, W.; Dastoor, P. C.; Zhou, X., Organic Thin-Film Transistor (OTFT)-Based Sensors. Electronics 2014, 3, 234-254.
7. Lin, P.; Yan, F., Organic Thin-Film Transistors for Chemical and Biological Sensing. Adv. Mater. 2012, 24, 34-51.
8. Mulla, M. Y.; Tuccori, E.; Magliulo, M.; Lattanzi, G.; Palazzo, G.; Persaud, K.; Torsi, L., Capacitance-modulated transistor detects odorant binding protein chiral interactions. Nat. Commun. 2015, 6, 6010.
9. Palazzo, G.; De Tullio, D.; Magliulo, M.; Mallardi, A.; Intranuovo, F.; Mulla, M. Y.; Favia, P.; Vikholm-Lundin, I.; Torsi, L., Detection Beyond Debye's Length with an Electrolyte-Gated Organic Field-Effect Transistor. Adv. Mater. 2015, 27, 911-916.
10. Torsi, L.; Magliulo, M.; Manoli, K.; Palazzo, G., Organic field-effect transistor sensors: a tutorial review. Chem. Soc. Rev. 2013, 42, 8612-8628.
11. Tarabella, G.; Mahvash Mohammadi, F.; Coppedè, N.; Barbero, F.; Iannotta, S.; Santato, C.; Cicoira, F., New opportunities for organic electronics and bioelectronics: ions in action. Chem. Sci. 2013, 4, 1395-1409.
12. Wang, Y.; Gong, Q.; Miao, Q., Structured and functionalized organic semiconductors for chemical and biological sensors based on organic field effect transistors. Mater. Chem. Front. 2020, 4 (12), 3505-3520.
13. Knopfmacher, 0.; Hammock, M. L.; Appleton, A. L.; Schwartz, G.; Mei, J.; Lei, T.; Pei, J.; Bao, Z., Highly stable organic polymer field-effect transistor sensor for selective detection in the marine environment. Nat. Commun. 2014, 5, 2954.
14. Li, H.; Shi, W.; Song, J.; Jang, H.-J.; Dailey, J.; Yu, J.; Katz, H. E., Chemical and Biomolecule Sensing with Organic Field-Effect Transistors. Chem. Rev. 2019, 119, 3-35.
15. Langton, M. J.; Serpell, C. J.; Beer, P. D., Anion Recognition in Water: Recent Advances from a Supramolecular and Macromolecular Perspective. Angew. Chem. Int. Ed. 2016, 55, 1974-1987.
16. Hua, Y.; Flood, A. H., Click chemistry generates privileged CH hydrogen-bonding triazoles: the latest addition to anion supramolecular chemistry. Chem. Soc. Rev. 2010, 39, 1262-1271.
17. Zahran, E. M.; Fatila, E. M.; Chen, C.-H.; Flood, A. H.; Bachas, L. G., Cyanostar: C—H Hydrogen Bonding Neutral Carrier Scaffold for Anion-Selective Sensors. Anal. Chem. 2018, 90, 1925-1933.
18. Cai, J.; Sessler, J. L., Neutral CH and cationic CH donor groups as anion receptors. Chem. Soc. Rev. 2014, 43, 6198-6213.
19. Lee, S.; Chen, C.-H.; Flood, A. H., A pentagonal cyanostar macrocycle with cyanostilbene CH donors binds anions and forms dialkylphosphate [3]rotaxanes. Nat. Chem. 2013, 5, 704-710.