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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Luminescence and Nonlinear Optical Properties of Hybrid Associates of Ag{sub 2}S Quantum Dots with Molecules of Thiazine Dyes

Spectral, kinetic, and nonlinear optical regularities that demonstrate the exchange of electronic excitations between the components of hybrid associates of Ag{sub 2}S colloid quantum dots (1.7–1.8 nm) in gelatin with molecules of thiazine dyes (Ds) are found. When the IR luminescence of Ag{sub 2}S quantum dots (QDs) is excited by radiation from the thionine absorption region, its enhancement due to nonradiative resonant energy transfer is observed. The association with methylene-blue molecules blocked the IR luminescence of Ag{sub 2}S QDs upon its excitation by radiation from the absorption region of the dye due to the transfer of charge carriers. It is demonstrated that the hybrid association of thionine molecules and Ag{sub 2}S QDs adversely affects the nonlinear optical properties of the latter, which manifests itself in inverse saturated absorption by the action of 10-ns second-harmonic pulses (532 nm) of a Nd{sup 3+}:YAG laser. For the associates of Ag{sub 2}S QDs with methylene-blue molecules, the radiation focusing caused by the transfer of charge carriers from the dye and the change in the population of small traps in nanocrystals is found. It is concluded that the direction of the transfer of electronic excitations and the photophysical processes in these objects are determined by the mutual arrangement of the HOMO–LUMO levels of the dye with respect to the levels of dimensional quantization of the Ag{sub 2}S QDs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Luminescent Properties of Hybrid Nanostructures Based on Quantum Dots of CdS, Europium 1,3-Diketonate, and Methylene Blue Molecules

The luminescent properties of hybrid nanostructures constructed from colloidal quantum dots (QDs) of CdS passivated with thioglycolic acid, europium(III) tris(tenoyltrifluoroacetonate), and methylene blue dye molecules are studied. Spectral features typical for the formation of core/shell QDs of the CdS/CdS:Eu{sup 3+} type are found. It is noted that the adsorption of the europium complex at the QD interfaces and the formation of QDs of the CdS/TGA/Eu{sup 3+} are probable. Spectral patterns that reveal nonradiative energy transfer from the recombination luminescence centers of CdS QDs to the Eu{sup 3+} ions in the CdS/CdS:Eu{sup 3+} and CdS/TGA/Eu{sup 3+} structures are obtained. This is manifested in quenching the recombination luminescence of QDs and in the ignition of the intracentric luminescence of Eu{sup 3+}, which enhance with an increase in the concentration of the europium complex. When such structures are combined with methylene blue molecules, the half-width of the absorption spectra is found to increase by 10–15% with an unchanged position of the absorption band maximum. With an increase in the concentration of methylene blue molecules, decreases in the intensity of the recombination luminescence band of CdS QDs at a wavelength of 530 nm and in the luminescence intensity of Eu{sup 3+} ions and simultaneously the rise up of the fluorescence of methylene blue at a wavelength of about 675 nm are observed. At the same time, a decrease in the luminescence lifetime of the bands of QDs and europium ions are observed. It is concluded that the nonradiative excitation energy transfer from both the recombination luminescence centers and Eu{sup 3+} ions to methylene blue molecules takes place.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Dynamics of photoprocesses induced by femtosecond infrared radiation in free molecules and clusters of iron pentacarbonyl

The dynamics of photoprocesses induced by femtosecond infrared radiation in free Fe(CO){sub 5} molecules and their clusters owing to the resonant excitation of vibrations of CO bonds in the 5-μm range has been studied. The technique of infrared excitation and photoionization probing (λ = 400 nm) by femtosecond pulses has been used in combination with time-of-flight mass spectrometry. It has been found that an infrared pulse selectively excites vibrations of CO bonds in free molecules, which results in a decrease in the yield of the Fe(CO){sub 5}{sup +} molecular ion. Subsequent relaxation processes have been analyzed and the results have been interpreted. The time of the energy transfer from excited vibrations to other vibrations of the molecule owing to intramolecular relaxation has been measured. The dynamics of dissociation of [Fe(CO){sub 5}]{sub n} clusters irradiated by femtosecond infrared radiation has been studied. The time dependence of the yield of free molecules has been measured under different infrared laser excitation conditions. We have proposed a model that well describes the results of the experiment and makes it possible, in particular, to calculate the profile of variation of the temperature of clusters within the “evaporation ensemble” concept. The intramolecular and intracluster vibrational relaxation rates in [Fe(CO){sub 5}]{sub n} clusters have been estimated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Electron Polarization Solitons in a Helical Molecule

The evolution of the spin of an electron moving along the axis of a long helical molecule under the action of an external field is investigated. The field is produced by the dipoles of individual molecules forming a complex molecular structure (e.g., a DNA molecule). The electron polarization dynamics associated with the spin–orbit interaction is described using an integrable generalization of the Manakov equations. The phase cross-modulation, self-modulation, and analogs of the Rashba and Dresselhaus Hamiltonians are taken into account in the model Hamiltonian. The corresponding apparatus based on the solution of the Riemann–Hilbert problem is used for obtaining soliton solutions. The resultant one- and two-soliton solutions demonstrate a number of new properties. It is shown that a local perturbation produces a selective effect on the soliton polarization and can be used for controlling the position of the electron spin using impurity molecules or quantum dots with a constant dipole moment. It is found that the spin–orbit interaction leads to a strong spatial modulation of the soliton shape. The collision of solitons leads to modulation transfer between solitons and a change in the modulation amplitude.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Dynamics of a Diatomic Molecule in a Trap

The dynamics of a diatomic molecule possessing translational, rotational, and vibrational degrees of freedom in a trap has been analyzed theoretically and numerically. The interaction of atoms in the molecule is described by the Lennard-Jones potential, while the interaction of atoms with the trap walls is described by an exponential potential of repulsion. The motion of a molecule away from the trap walls can be reduced to the classical two-body problem with the central interaction and is regular. It has been established that an intense interaction of atoms of the molecule with the trap walls leads to stochastization of motion.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

An initial investigation of accuracy required for the identification of small molecules in complex samples using quantum chemical calculated NMR chemical shifts

The majority of primary and secondary metabolites in nature have yet to be identified, representing a major challenge for metabolomics studies that currently require reference libraries from analyses of authentic compounds. Using currently available analytical methods, complete chemical characterization of metabolomes is infeasible for both technical and economic reasons. For example, unambiguous identification of metabolites is limited by the availability of authentic chemical standards, which, for the majority of molecules, do not exist. Computationally predicted or calculated data are a viable solution to expand the currently limited metabolite reference libraries, if such methods are shown to be sufficiently accurate. For example, determining nuclear magnetic resonance (NMR) spectroscopy spectra in silico has shown promise in the identification and delineation of metabolite structures. Many researchers have been taking advantage of density functional theory (DFT), a computationally inexpensive yet reputable method for the prediction of carbon and proton NMR spectra of metabolites. However, such methods are expected to have some error in predicted 13 >C and 1 H NMR spectra with respect to experimentally measured values. This leads us to the question–what accuracy is required in predicted 13 C and 1 H NMR chemical shifts for confident metabolite identification? Using the set of 11,716 small molecules found in the Human Metabolome Database (HMDB), we simulated both experimental and theoretical NMR chemical shift databases. We investigated the level of accuracy required for identification of metabolites in simulated pure and impure samples by matching predicted chemical shifts to experimental data. We found 90% or more of molecules in simulated pure samples can be successfully identified when errors of 1 H and 13 C chemical shifts in water are below 0.6 and 7.1 ppm, respectively, and below 0.5 and 4.6 ppm in chloroform solvation, respectively. In simulated complex mixtures, as the complexity of the mixture increased, greater accuracy of the calculated chemical shifts was required, as expected. However, if the number of molecules in the mixture is known, e.g., when NMR is combined with MS and sample complexity is low, the likelihood of confident molecular identification increased by 90%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Ultracold Molecules: Physics in the Quantum Regime

Our research encompasses approaches to the trapping of diatomic molecules at low temperature plus the cooling and detection of polyatomic molecules in the kelvin temperature regime. We have cooled and trapped CaF and/or CaH molecules, loaded directly from a molecular beam. As part of this work, we are continuing to develop an important trapping technique, optical loading from a buffer-gas beam. This method was invented in our lab. We are also studying cold polyatomic molecules and their interactions with cold atoms.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Identifying Performance Advantaged Biobased Chemicals Utilizing Bioprivileged Molecules

Two technology areas were advanced; a) novel molecules with improved performance in the end use application of organic corrosion inhibitors and flame retardant nylon polymers and b) development of a systematic process for identifying biomass-derived molecules with improved performance in end use applications. In total 17 novel organic corrosion inhibitors were identified that had significantly better performance than the commercial reference organic corrosion inhibitor and 7 novel nylons were synthesized with improved flame retardant properties relative to standard nylon-6,6. While an end-to-end systematic process for identifying biomass-derived molecules with improved end use performance was not completed, important progress was made computational tools for mining chemical structures from the literature and databases as well as establishing reaction network generation algorithms to aid in the discovery of novel molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Statistically-driven Experimental Design to Improve Reference-free Quantification of Small Molecules by Liquid Chromatography-Mass Spectrometry

Non-targeted analysis of small molecules and metabolites in unknown, complex samples using liquid chromatography-tandem mass spectrometry remains challenging. One of the main bottlenecks is the extensive unannotated regions of metabolomics mass spectrometry data, resulting in knowledge gaps. Small molecule annotation in mass spectrometry data has conventionally relied on reference standards and libraries for compound identification and confirmation, which can constrain compound identification to those molecules already known, thus limiting the ability to discover new knowledge and new markers. Retention time prediction can facilitate and expedite unknown compound identification in non-targeted analysis of complex metabolomics samples. Additionally, accurate retention time predictions can also inform sample mixture design for LC-MS/MS analyses. However, current machine learning-based methods for retention time prediction are typically developed for specific chromatographic platforms and are not generalizable across scales. And while technologies and methods to improve reference-free metabolite identification for more comprehensive annotation of unknowns has received much attention, development of the same for quantitation without reference standards has been much more limited, despite its importance in toxicological, environmental, food safety, forensics, and clinical applications. We believe that a reference-free quantitation strategy that exploits mass spectrometry data already collected for reference-free identification can provide much more insight on unknowns, and move the metabolomics field for more complete unknowns characterization. As such, we pursue two efforts to improve upon current state-of-the-art methods in non-targeted analysis: (1) machine learning-based retention time prediction and (2) statistical design of experiments framework for reference-free quantitation. In this work, we develop and demonstrate (1) a generalizable retention time prediction capability across chromatographic conditions and scales, and (2) a statistical design-based framework for response factor contribution elucidation and reference-free quantitation. Evaluation of our retention time prediction model, PrediToR, showed approximately 24% improvement over current models, and we observed approximately 10X improvement in concentration estimation accuracy from our statistical design-based response factor model over a primarily ionization efficiency-based model. We expect that future efforts to improve upon these new capabilities will further advance non-targeted analysis of small molecules towards truly reference-free metabolomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Laser Spectroscopy of Exotic Atoms and Molecules Containing Octupole-Deformed Nuclei

This project investigated the nuclear, atomic, and molecular structure of exotic atoms and molecules containing actinide isotopes. These short-lived radioactive systems are challenging to produce and study in the laboratory, yet they offer unique opportunities for fundamental science. These nuclei are predicted to exhibit pear-shaped (octupole) deformation, a rare collective nuclear behavior that dramatically enhances their sensitivity to fundamental physics phenomena such as time-reversal- and parity-violating effects. Such enhancements make them ideal probes for exploring open questions in our understanding of the universe such as the origin of the matter–antimatter asymmetry of the universe. To realize these measurements, the project led the development of a new laser spectroscopy experiment at MIT, and later commissioned at the Facility for Rare Isotope Beams (FRIB) at Michigan State University: the Resonance Ionization Spectroscopy Experiment (RISE). RISE combines the spectroscopic precision of collinear laser spectroscopy with the sensitivity of particle-detection techniques, enabling measurements of rare isotopes produced at rates as low as a few ions per second. The beamline was designed, built, and installed, and was successfully commissioned at FRIB during the grant period. RISE is now a permanent capability of the FRIB facility, and has produced several results on the study of rare atoms and molecules for nuclear structure and fundamental symmetries. In parallel with the FRIB program, the project contributed to the first precision laser-spectroscopy measurements of short-lived radioactive molecules. Working with international collaborators at CERN's ISOLDE facility, the team conducted pioneering experiments on radium monofluoride (RaF) and actinium monofluoride (AcF). The results from this work have been published in major journals of science, including Nature, Science, Nature Physics, Nature Communications, and Physical Review Letters. These findings have guided future experiments on the laser cooling of radioactive molecules, opening a new platform for precision tests of fundamental symmetries.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Hidden molecules in planetary nebulae: New detections of HCN and HCO{sup +} from a multi-object survey

Searches for HCN and HCO{sup +} have been conducted toward 17 planetary nebulae (PNs) in the age range 800 to 13,000 years using the facilities of the Arizona Radio Observatory (ARO). For both molecules, observations of the J=1→0 transition near 88–89 GHz were carried out with the ARO 12 m, including measurements with the new ALMA prototype antenna, while the J=3→2 lines near 265–267 GHz were sought with the ARO Sub-Millimeter Telescope (SMT). HCN and HCO{sup +} were newly detected in 13 of the 17 target sources in at least one transition. Nine PNs were common to both molecules: Hb5, K3-17, K3-58, M1-7, M4-14, M3-28, M3-55, NGC 2440, and K4-47, while HCO{sup +} was also identified in K3-83 and M2-9, and HCN in K3-45 and NGC 6772. From radiative transfer modeling, column densities for HCN and HCO{sup +} in these sources were determined to be N{sub tot}(HCN) ∼ 0.2–27 × 10{sup 13} cm{sup −2} and N{sub tot}(HCO{sup +}) ∼ 0.3–8.7 × 10{sup 13} cm{sup −2}. Gas densities, assumed to be in clumped regions, were established to be n(H{sub 2}) ∼ 0.1–5.2 × 10{sup 6} cm{sup −3}. Fractional abundances, relative to H{sub 2}, for both molecules were found to be f(HCN) ∼ 0.1–9.1 × 10{sup −7} and f(HCO{sup +}) ∼ 0.04–7.4 × 10{sup −7}. The abundances of both species were found to remain relatively constant with nebular age over a 10,000 year time span, in contrast to predictions of chemical models. The HCN/HCO{sup +} ratio varied from 17 to <0.2, and roughly correlates with the C/O ratio. Polyatomic molecules appear to be common constituents of PNs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

STICKING OF MOLECULES ON NONPOROUS AMORPHOUS WATER ICE

Accurate modeling of physical and chemical processes in the interstellar medium (ISM) requires detailed knowledge of how atoms and molecules adsorb on dust grains. However, the sticking coefficient, a number between 0 and 1 that measures the first step in the interaction of a particle with a surface, is usually assumed in simulations of ISM environments to be either 0.5 or 1. Here we report on the determination of the sticking coefficient of H{sub 2}, D{sub 2}, N{sub 2}, O{sub 2}, CO, CH{sub 4}, and CO{sub 2} on nonporous amorphous solid water. The sticking coefficient was measured over a wide range of surface temperatures using a highly collimated molecular beam. We showed that the standard way of measuring the sticking coefficient—the King–Wells method—leads to the underestimation of trapping events in which there is incomplete energy accommodation of the molecule on the surface. Surface scattering experiments with the use of a pulsed molecular beam are used instead to measure the sticking coefficient. Based on the values of the measured sticking coefficient, we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy. We use this formula in a simulation of ISM gas–grain chemistry to find the effect of sticking on the abundance of key molecules both on grains and in the gas phase.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

Theoretical Calculation for the Ionization of Molecules by Short Strong Laser Pulses

We have developed several calculation methods for the ionization of atoms and molecules by strong and ultrashort laser pulses, based on the numerical solution of the time dependent Schroedinger equation (TDSE) in the momentum space. We have performed calculations within the strong field approximation (Volkov) and using iterative and direct methods for solving the TDSE. The investigated molecules are H{sub 2}{sup +} and H{sub 2}O. In case of the ionization of diatomic molecules the interference effects in the ejected electron spectra due to the coherent addition of the waves associated to the electrons ejected from the vicinity of different nuclei were also analysed.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Effect of electrode spacing on the density distributions of electrons, ions, and metastable and radical molecules in SiH{sub 4}/NH{sub 3}/N{sub 2}/He capacitively coupled plasmas

Semiconductor fabrication often requires the deposition of hydrogenated silicon nitride (SiN{sub x}H{sub y}) film using SiH{sub 4}/NH{sub 3}/N{sub 2}/He capacitively coupled plasma (CCP) discharge. As analysis of the discharge geometry is essential to understanding CCP deposition, the effect of electrode spacing on the two-dimensional distributions of electrons, ions, and metastable and radical molecules was analyzed numerically using a fluid model. The simulation shows that the spatial variations in the ionization rates near the sheath become more obvious as the electrode spacing increases. In addition, as molecule-molecule gas-phase reactions are significantly affected by the local residence time, large electrode spacings are associated with significant volumetric losses for positive ions. Consequently, an increase of the electrode spacing leads axial density profiles of ions to change from bell shaped to double humped. However, NH{sub 4}{sup +} persistently maintains a bell-shaped axial density profile regardless of the degree of electrode spacing. We set the mole fraction of NH{sub 3} to only 1% of the total flow at the inlet, but NH{sub 4}{sup +} is the most abundant positive ion at the large electrode spacings. As the gas flow can transport the radicals around the space between the electrodes, we found that radical density distribution shifts toward the grounded electrode. The shift becomes pronounced as the electrode spacing increases. Finally, to validate our model, we compared the calculated deposition rate profile with the experimental data obtained along the wafer radius. According to our numerical results, the SiN{sub x}H{sub y} deposition rate decreases by approximately 16% when the electrode spacing increases from 9 to 20 mm.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Site-Selective Catalysis of a Multifunctional Linear Molecule: The Steric Hindrance of Metal–Organic Framework Channels

The site-selective reaction of a multifunctional linear molecule requires a suitable catalyst possessing both uniform narrow channel to limit the molecule rotation and a designed active site in the channel. Recently, nanoparticles (NPs) were incorporated in metal–organic frameworks (MOFs) with the tailorable porosity and ordered nanochannel, which makes these materials (NPs/MOFs) highly promising candidates as catalytic nanoreactors in the field of heterogeneous catalysis. Inspired by a “Gondola” sailing in narrow “Venetian Canal” without sufficient space for a U-turn, a simple heterogeneous catalyst based on NPs/MOFs is developed here that exhibits site-selectivity for the oxidation of diols by restricting the random rotation of the molecule (the “Gondola”) in the limited space of the MOF channel (the narrow “Venetian Canal”), thereby protecting the middle functional group via steric hindrance. This strategy is not limited to the oxidation of diols, but can be extended to the site-selective reaction of many similar multifunctional linear molecules, such as the reduction of alkadienes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Symmetry‐Breaking Strategy Yields Dopant‐Free Small Molecule Hole Transport Materials for Inorganic Perovskite Solar Cells with 20.58% Efficiency and Outstanding Stability

Abstract Inorganic perovskites are known for their excellent photothermal stability; however, the photothermal stability of all‐inorganic n‐i‐p perovskite solar cells (PSCs) is compromised due to ion diffusion and free radical‐induced degradation caused by the use of doped spiro‐OMeTAD hole transport materials (HTMs). In this study, two isomeric donor–acceptor–donor (D–A–D) type small molecules, namely HBT and HiBT, were developed and used as dopant‐free HTMs, using 2,1,3‐benzothiadiazole or benzo[d][1,2,3]thiadiazole as acceptor moieties. The HiBT molecule, with its symmetry‐breaking features, exhibits a large dipole moment, enhanced coordination‐active sites, and a well‐aligned energy level structure, all of which contribute to passivating perovskite surface defects and improving free charge separation. As a result, inorganic CsPbI 3 PSCs with HiBT HTM achieved an impressive power conversion efficiency (PCE) of 20.58%, the highest reported for dopant‐free HTM‐based inorganic PSCs. Moreover, the enhanced hydrophobic properties of HiBT molecules, coupled with their ability to passivate perovskite surface defects, contribute to significantly improved device stability. The unencapsulated devices based on HiBT HTM retained over 83% and 80% of their initial efficiency after being stored at 85 °C for 50 days and undergoing maximum power point (MPP) tracking at 85 °C for 1100 h, respectively. These results highlight that the symmetry‐breaking strategy is an exceptionally effective approach for designing efficient, dopant‐free small molecule HTMs, significantly contributing to both the high efficiency and enhanced stability of all‐inorganic PSCs.

Chemistry↗
DOE OSTI2020

Insights from 20 years of the Molecule of the Month

For 20 years, Molecule of the Month articles have highlighted the functional stories of 3D structures found in the Protein Data Bank (PDB). The PDB is the primary archive of atomic structures of biological molecules, currently providing open access to more than 150,000 structures studied by researchers around the world. The wealth of knowledge embodied in this resource is remarkable, with structures that allow exploration of nearly any biomolecular topic, including the basic science of genetic mechanisms, mechanisms of photosynthesis and bioenergetics, and central biomedical topics like cancer therapy and the fight against infectious disease. The central motivation behind the Molecule of the Month is to provide a user-friendly introduction to this rich body of data, charting a path for users to get started with finding and exploring the many available structures. The Molecule of the Month and related materials are updated regularly at the education portal PDB-101 (http://pdb101.rcsb.org/), offering an ongoing resource for molecular biology educators and students around the world.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn 2+ ion in (TMC)Fe III -(O 2 )-Zn(CF 3 SO 3 ) 2 (1-Zn 2+ ) decreases the Lewis acidity of the Zn 2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn 2+ . This further changes the reactivities of 1-Zn 2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn 2+ , whereas 1-Zn 2+ coordinating two water molecules, (TMC)Fe III -(O 2 )-Zn(CF 3 SO 3 ) 2 -(OH 2 ) 2 [1-Zn 2+ -(OH 2 ) 2 ], releases the O 2 unit in the oxidation reaction. In the reduction reactions, 1-Zn 2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn 2+ -(OH 2 ) 2 . Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗