A method for depositing a metal layer includes a step of contacting a surface of an electrically conductive substrate with a vapor of a metal-containing compound for a first predetermined pulse time to form a modified surface on the electrically conductive substrate. The metal-containing compound is a metal diketonate or a structurally similar compound. The modified surface is contacted with a vapor of a reducing agent that is a hydrazine or a hydrazine derivative for a second predetermined pulse time to form a metal-containing film on the surface of the electrically conductive substrate. Characteristically, the metal-containing film includes the metal atom in a zero oxidation state in an amount greater than 80 mole percent.

Provided herein are fluoro-substituted porphyrin compounds, such as those having a structure represented by Formula (I), wherein R.sup.1 is a C1-C8 alkyl that is substituted with at least 1 fluorine (e.g., a C1-C8 alkyl substituted with 1-17 fluorine atoms); and X is an anion (e.g. a halogen ion (e.g., chloride, etc.), PF.sub.6, tosylate, besylate, and/or mesylate). Also provided herein are methods of making the fluoro-substituted porphyrin compounds, pharmaceutical formulations containing the same, and methods of use thereof.

Conjugates derived from non-steroidal anti-inflammatory drugs (NSAIDs) and methods of use thereof are disclosed, useful for, inter alia, identifying and localizing the site of pathology and/or inflammation responsible for the sensation of pain in a patient; for identifying the sites of primary, secondary, benign, or malignant tumors; and for diagnosing infection or confirming or ruling out suspected infection. The NSAID-based conjugates contain an imaging moiety. The conjugates concentrate at sites of increased cyclooxygenase expression, thus revealing the sites of increased prostaglandin production, which is correlated with pain and inflammation, and correlated with tumor presence and/or location. Identifying areas of increased COX expressing can also aid in screening for infections.

Aspects of the present disclosure relate to compounds which have enhanced oral bioavailability. A transition metal complex includes a transition metal coordinated by a macrocycle comprising the pentaaza 15-membered macrocyclic ring corresponding to Formula A and two axial ligands having the formula —OC(O)X.sub.1.

##STR00001## each of the two axial ligands has the formula —OC(═O)X.sub.1 wherein each X.sub.1 is independently substituted or unsubstituted phenyl or —C(—X.sub.2)(—X.sub.3)(—X.sub.4); each X.sub.2 is independently substituted or unsubstituted phenyl, or substituted or unsubstituted alkyl; each X.sub.3 is independently hydrogen, hydroxyl, alkyl, amino, —X.sub.5C(═O)R.sub.13 where X.sub.5 is NH or O, and R.sub.13 is C.sub.1-C.sub.18 alkyl, substituted or unsubstituted aryl or C.sub.1-C.sub.18 aralkyl, or —OR.sub.14, where R.sub.14 is C.sub.1-C.sub.18 alkyl, substituted or unsubstituted aryl or C.sub.1-C.sub.18 aralkyl, or together with X.sub.4 is (═O); and each X.sub.4 is independently hydrogen or together with X.sub.3 is (═O).

Through the use of a rhodamine appended chelate, a versatile strategy has been demonstrated to generate mitochondria-targeting photosensitizers via the incorporation of variety of luminescent transition metal systems. The generation of triplet excited state of rhodamine moiety endows the complexes with mitochondria-targeting photosensitizing ability to form singlet oxygen (.sup.1O.sub.2) for use as photodynamic therapy (PDT) agent. The combination of rhodamine organic dye and luminescent transition metal centers in such hybrid systems exhibits the synergistic merits, including low dark cytotoxicity, selective tumor cell uptake, high molar absorptivity for low-energy excitation in the visible region, and high photostability.

Through the use of a rhodamine appended chelate, a versatile strategy has been demonstrated to generate mitochondria-targeting photosensitizers via the incorporation of variety of luminescent transition metal systems. The generation of triplet excited state of rhodamine moiety endows the complexes with mitochondria-targeting photosensitizing ability to form singlet oxygen (.sup.1O.sub.2) for use as photodynamic therapy (PDT) agent. The combination of rhodamine organic dye and luminescent transition metal centers in such hybrid systems exhibits the synergistic merits, including low dark cytotoxicity, selective tumor cell uptake, high molar absorptivity for low-energy excitation in the visible region, and high photostability.

The present invention relates to compounds of Formula I:

##STR00001##

wherein R.sup.1, L.sup.1, A, X.sup.a, L.sup.2, B and X.sup.b are each as defined herein. The present invention also relates to compounds of Formula II and III defined herein, formed by self-assembly of the compounds of Formula I with a metal M and an anion Q. Compounds of Formula II and III are useful in the treatment of proliferative disorders, such as cancer. The present invention also relates to pharmaceutical compositions comprising compounds of Formula I, II or III, and to the use of these compounds and compositions in the treatment of proliferative disorders, such as cancer.

Non-d.sup.0 rhenium(V) alkylidyne catalysts useful for catalyzing alkyne metathesis reactions, such as homo- and cross-metathesis of alkynes or diynes, ring closing metathesis and ring-opening metathesis, methods or use, and preparation thereof. The catalysts are stable to air and moisture and tolerate a variety of functional groups in substrates.

Non-d.sup.0 rhenium(V) alkylidyne catalysts useful for catalyzing alkyne metathesis reactions, such as homo- and cross-metathesis of alkynes or diynes, ring closing metathesis and ring-opening metathesis, methods or use, and preparation thereof. The catalysts are stable to air and moisture and tolerate a variety of functional groups in substrates.

Compounds are synthesized with bicyclic amidinate ligands attached to one or more metal atoms. These compounds are useful for the synthesis of materials containing metals. Examples include pure metals, metal alloys, metal oxides, metal nitrides, metal phosphides, metal sulfides, metal selenides, metal tellurides, metal borides, metal carbides, metal silicides and metal germanides. Techniques for materials synthesis include vapor deposition (chemical vapor deposition and atomic layer deposition), liquid solution methods (sol-gel and precipitation) and solid-state pyrolysis. Copper metal films are formed on heated substrates by the reaction of copper(I) bicyclic amidinate vapor and hydrogen gas, whereas reaction with water vapor produces copper oxide. Silver and gold films were deposited on surfaces by reaction of their respective bicyclic amidinate vapors with hydrogen gas. Reaction of cobalt(II) bis(bicyclic amidinate) vapor, ammonia gas and hydrogen gas deposits cobalt metal films on heated substrates, while reaction with ammonia produces cobalt nitride and reaction with water vapor produces cobalt oxide. Ruthenium metal films are deposited by reaction of ruthenium(II) bis(bicyclic amidinate) or ruthenium(III) tris(bicyclic amidinate) at a heated surface either with or without a co-reactant such as hydrogen gas or ammonia or oxygen. Suitable applications include electrical interconnects in microelectronics and magnetoresistant layers in magnetic information storage devices. Hafnium oxide films are deposited by reaction of hafnium(IV) tetrakis(bicyclic amidinate) with oxygen sources such as water, hydrogen peroxide or ozone. The HfO.sub.2 films have high dielectric constant and low leakage current, suitable for applications as an insulator in microelectronics. The films have very uniform thickness and complete step coverage in narrow holes.