Abstract: The present disclosure features a condensation reaction and a luciferin-unmasking reaction that can be carried out under physiological conditions. In general, the condensation reaction involves reacting a bicyclic reactant with an aminothiol derivative, generating a luciferin or luciferin derivative. A luciferin can provide detectable luminescence. A luciferin derivative can be unmasked to provide detectable luminescence in a luciferin-unmasking reaction. The present disclosure provides bicyclic reactants and aminothiol derivatives suitable for use in the condensation reaction. The condensation and luciferin-unmasking reactions find use in a variety of applications, which are also provided.

Abstract: Chemoselective conjugation is achieved through redox reactivity by reacting an N-transfer oxidant with a thioether substrate in a redox reaction in an aqueous environment to form a conjugation product. In embodiments, Redox-Activated Chemical Tagging (ReACT) strategies for methionine-based protein functionalization. Oxaziridine (Ox) compounds serve as oxidant-mediated reagents for direct functionalization by converting methionine to the corresponding sulfimide conjugation product.

Abstract: The present disclosure features a condensation reaction and a luciferin-unmasking reaction that can be carried out under physiological conditions. In general, the condensation reaction involves reacting a bicyclic reactant with an aminothiol derivative, generating a luciferin or luciferin derivative. A luciferin can provide detectable luminescence. A luciferin derivative can be unmasked to provide detectable luminescence in a luciferin-unmasking reaction. The present disclosure provides bicyclic reactants and aminothiol derivatives suitable for use in the condensation reaction. The condensation and luciferin-unmasking reactions find use in a variety of applications, which are also provided.

Abstract: The present disclosure provides compositions for in vivo imaging of hydrogen peroxide; and methods for detecting hydrogen peroxide in vivo. The compositions and methods find use in various diagnostic applications, which are also provided.

Abstract: The present invention provides for a composition comprising a heterostructure capable of electrochemical CO reduction to a carbon-carbon product, comprising an inorganic material and a porous molecule.

Abstract: This disclosure provides systems, methods, and apparatus related to artificial photosynthesis. In one aspect a system includes a photoanode chamber including a photoanode assembly, a photocathode chamber including a photocathode assembly, an electrical connection electrically connecting the photoanode assembly and the photocathode assembly, a membrane separating the photoanode chamber and the photocathode chamber, and a microorganism disposed in the photocathode chamber. The photoanode assembly is operable to oxidize water to generate oxygen, protons, and electrons. The membrane is permeable to the protons and operable to allow the protons to travel to the photocathode chamber. The electrical connection provides electrons to the photocathode assembly. The microorganism comprises a metabolic pathway to reduce carbon dioxide and to generate a carbon-based compound using the electrons or hydrogen formed by two protons.

Abstract: Probes for formaldehyde (FA) including a homoallylamine trigger group attached to a detectable moiety are provided. Aspects of the probes include luminogenic or fluorogenic probes, such as a probe including a quencher in energy-receiving proximity to a fluroophore. Also provided are methods of using the probes for sensitive and bio orthogonal detection of FA in a sample. Aspects of the methods include selectively reacting the probe with the formaldehyde in the sample to a release (e.g., via a 2-aza-Cope rearrangement) a reporter group comprising a detectable moiety. Aspects of the methods detecting formaldehyde in a cell, tissue, organ or fluid in a subject. Also provided are compositions and kits including the subject probes that find use in practicing various embodiments of the subject methods.

Abstract: A method of selective detection of a concentration of a metal ion species in a subject is provided in which a biofluid sample is obtained from the subject. The biofluid sample is exposed to a functionalized porous aromatic polymer. The polymer selectively captures and concentrates the metal ion species from the biofluid. Subsequently, the biofluid is washed from the polymer. The polymer is then exposed to a solution comprising a colorimetric indicator that extracts the metal ion species from the washed polymer thereby changing a color of the solution as a function of an amount of the metal ion species in the polymer. The concentration of the metal ion species in the subject is then spectroscopically determined from the color of the solution.

Abstract: The present disclosure provides compositions for in vivo imaging of hydrogen peroxide; and methods for detecting hydrogen peroxide in vivo. The compositions and methods find use in various diagnostic applications, which are also provided.

Abstract: New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W2)MoS2]x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H2 per mole of catalyst.

Abstract: This disclosure provides systems, methods, and apparatus related to artificial photosynthesis. In one aspect a system includes a photoanode chamber including a photoanode assembly, a photocathode chamber including a photocathode assembly, an electrical connection electrically connecting the photoanode assembly and the photocathode assembly, a membrane separating the photoanode chamber and the photocathode chamber, and a microorganism disposed in the photocathode chamber. The photoanode assembly is operable to oxidize water to generate oxygen, protons, and electrons. The membrane is permeable to the protons and operable to allow the protons to travel to the photocathode chamber. The electrical connection provides electrons to the photocathode assembly. The microorganism comprises a metabolic pathway to reduce carbon dioxide and to generate a carbon-based compound using the electrons or hydrogen formed by two protons.

Abstract: Carbon monoxide (CO) is a member of the gasotransmitter family that includes NO and H2S and is implicated in a variety of pathological and physiological conditions. Whereas exogenous therapeutic additions of CO to tissues and whole animals have been well studied, the real-time spatial and temporal tracking of CO at the cellular level remains an open challenge. We now report a new type of turn-on fluorescent probe for selective CO detection by exploiting palladium-mediated carbonylation reactivity. The compounds of the invention are capable of detecting CO both in aqueous buffer and in live cells with high selectivity over a range of biologically relevant reactive small molecules, providing a potentially powerful approach for interrogating its chemistry in biological systems.

Abstract: New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W2)MoS2]x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H2 per mole of catalyst.

Abstract: The present disclosure features a condensation reaction and a luciferin-unmasking reaction that can be carried out under physiological conditions. In general, the condensation reaction involves reacting a bicyclic reactant with an aminothiol derivative, generating a luciferin or luciferin derivative. A luciferin can provide detectable luminescence. A luciferin derivative can be unmasked to provide detectable luminescence in a luciferin-unmasking reaction. The present disclosure provides bicyclic reactants and aminothiol derivatives suitable for use in the condensation reaction. The condensation and luciferin-unmasking reactions find use in a variety of applications, which are also provided.

Abstract: New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W2)MoS2]x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H2 per mole of catalyst.

Abstract: The invention provides reaction-based fluorescent probes for selective imaging of hydrogen sulfide in living cells.

Abstract: The present disclosure features a condensation reaction and a luciferin-unmasking reaction that can be carried out under physiological conditions. In general, the condensation reaction involves reacting a bicyclic reactant with an aminothiol derivative, generating a luciferin or luciferin derivative. A luciferin can provide detectable luminescence. A luciferin derivative can be unmasked to provide detectable luminescence in a luciferin-unmasking reaction. The present disclosure provides bicyclic reactants and aminothiol derivatives suitable for use in the condensation reaction. The condensation and luciferin-unmasking reactions find use in a variety of applications, which are also provided.

Abstract: Carbon monoxide (CO) is a member of the gasotransmitter family that includes NO and H2S and is implicated in a variety of pathological and physiological conditions. Whereas exogenous therapeutic additions of CO to tissues and whole animals have been well studied, the real-time spatial and temporal tracking of CO at the cellular level remains an open challenge. We now report a new type of turn-on fluorescent probe for selective CO detection by exploiting palladium-mediated carbonylation reactivity. The compounds of the invention are capable of detecting CO both in aqueous buffer and in live cells with high selectivity over a range of biologically relevant reactive small molecules, providing a potentially powerful approach for interrogating its chemistry in biological systems.

Abstract: A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition having the general formula [(PY5W2)MO]2+, wherein PY5W2 is (NC5XYZ)(NC5H4)4C2W2, M is a transition metal, and W, X, Y, and Z can be H, R, a halide, CF3, or SiR3, where R can be an alkyl or aryl group. The two accompanying counter anions, in one embodiment, can be selected from the following Cl?, I?, PF6?, and CF3SO3?. In embodiments of the invention, water, such as tap water containing electrolyte or straight sea water can be subject to an electric potential of between 1.0 V and 1.4 V relative to the standard hydrogen electrode, which at pH 7 corresponds to an overpotential of 0.6 to 1.0 V, with the result being, among other things, the generation of hydrogen with an optimal turnover frequency of ca. 1.5 million mol H2/mol catalyst per h.

Abstract: The invention provides fluorescent sensors for the selective detection of a metal such as copper. The sensors may be considered to be derivatives of cyanine, fluorescein, rhodamine, rhodol, Tokyo green, or BODIPY. The sensors find particular use in detecting copper in cells and living animals.