Photodriven oxidations of alkanes in trifluoroacetic acid using commercial and synthesized Fe(III) sources as catalyst precursors and dioxygen (O2) as the terminal oxidant are reported. The reactions produce alkyl esters and occur at ambient temperature in the presence of air, and catalytic turnover is observed for the oxidation of methane in a pure O2 atmosphere. Under optimized conditions, approximately 17% conversion of methane to methyl trifluoroacetate at more than 50% selectivity is observed. It is demonstrated that methyl trifluoroacetate is stable under catalytic conditions, and thus overoxidized products are not formed through secondary oxidation of methyl trifluoroacetate.Optically driven ordering transitions are rarely observed in macromolecular systems, often because of kinetic limitations. Here, we report a series of block co-oligomers (BCOs) that rapidly order and disorder at room temperature in response to optical illumination, and the absence thereof. The system is a triblock where rigid azobenzene (Azo) mesogens are attached to each end of a flexible siloxane chain. UV-induced trans-to-cis Azo isomerization, and vice versa in the absence of UV light, drive disordering and ordering of lamellar superstructures and smectic mesophases, as manifested by liquefaction and solidification of the material, respectively. The impacts of chemical structure on BCO self-assembly and photoswitching kinetics are explored by in situ microscopy and X-ray measurements for different mesogen end groups (NO2 or CN), and different carbon chain lengths (0C or 12C) between the siloxane and the mesogen. The presence of the 12C spacer leads to hierarchical ordering with smectic layers of mesogens existing alongside larger length-scale lamellae, versus only smectic ordering without the spacer. These hierarchically ordered BCOs display highly persistent lamellar sheets that contrast with the tortuous, low-persistence “fingerprint”-type structures seen in conventional block copolymers. The reordering kinetics upon removal of UV illumination are extremely rapid ( less then 5 s). This fast response is due to the electron-withdrawing NO2 and CN, which facilitate cis-to-trans isomerization via thermal relaxation at room temperature without additional stimuli. This work elucidates structure-property relationships in photoswitching BCOs and advances the possibility of developing systems in which ordered nanostructures can be easily optically written and erased.The increasing occurrence of harmful algal blooms (HABs) in surface waters may increase the input of algal organic matter (AOM) in drinking water. The formation of halogenated disinfection byproducts (DBPs) during combined chlorination and chloramination of AOM and natural organic matter (NOM) in the presence of bromide and iodide and haloform formation during halogenation of model compounds were studied. Results indicated that haloform/halogen consumption ratios of halogens reacting with amino acids (representing proteins present in AOM) follow the order iodine > bromine > chlorine, with ratios for iodine generally 1-2 orders of magnitude greater than those for chlorine (0.19-2.83 vs 0.01-0.16%). This indicates that iodine is a better halogenating agent than chlorine and bromine. In contrast, chlorine or bromine shows higher ratios for phenols (representing the phenolic structure of humic substances present in NOM). Consistent with these observations, chloramination of AOM extracted from Microcystis aeruginosa in the presence of iodide produced 3 times greater iodinated trihalomethanes than those from Suwannee River NOM isolate. Cytotoxicity and genotoxicity of disinfected algal-impacted waters evaluated by Chinese hamster ovary cell bioassays both follow the order chloramination > prechlorination-chloramination > chlorination. This trend is in contrast to additive toxicity calculations based on the concentrations of measured DBPs since some toxic iodinated DBPs were not identified and quantified, suggesting the necessity of experimentally analyzing the toxicity of disinfected waters. During seasonal HAB events, disinfection practices warrant optimization for iodide-enriched waters to reduce the toxicity of finished waters.Direct conversion of methane to C2 compounds by oxidative and nonoxidative coupling reactions has been intensively studied in the past four decades; however, because these reactions have intrinsic severe thermodynamic constraints, they have not become viable industrially. Recently, with the increasing availability of inexpensive “green electrons” coming from renewable sources, electrochemical technologies are gaining momentum for reactions that have been challenging for more conventional catalysis. N6-methyladenosine manufacturer Using solid-state membranes to control the reacting species and separate products in a single step is a crucial advantage. Devices using ionic or mixed ionic-electronic conductors can be explored for methane coupling reactions with great potential to increase selectivity. Although these technologies are still in the early scaling stages, they offer a sustainable path for the utilization of methane and benefit from the advances in both solid oxide fuel cells and electrolyzers. This review identifies promising developments for solid-state methane conversion reactors by assessing multifunctional layers with microstructural control; combining solid electrolytes (proton and oxygen ion conductors) with active and selective electrodes/catalysts; applying more efficient reactor designs; understanding the reaction/degradation mechanisms; defining standards for performance evaluation; and carrying techno-economic analysis.The reaction of NO+ with water molecules plays a crucial role in the D-region of the atmosphere because the reaction provides nitrous acid (HONO) and protonated water species (H3O+). In this study, the reaction of NO+ with water clusters, NO+ + (H2O)n (n = 1-7), was investigated by means of the direct ab initio molecular dynamics method to elucidate the reaction mechanism of NO+ in the atmosphere from a theoretical viewpoint. At n = 1 and 2, the reaction of NO+ with (H2O)n led to the formation of a complex NO+ + (H2O)n → NO+(H2O)n (n = 1 and 2). At n = 3, the formation channel of HONO was open, and HONO was formed according to NO+ + (H2O)n → HONO—H+(H2O)n-1 (n = 3), through which H3O+ was also formed as H+(H2O)2. However, the HONO formation efficiency was significantly low for n = 3. In large clusters with n = 4-7, the HONO formation channel became the main channel, and the dissociation of HONO from the HONO–H+(H2O)n-1 complex occurred in part NO+ + (H2O)n → HONO—H+(H2O)n-1 → HONO + H+(H2O)n-1. The energetics and reaction mechanism were discussed on the basis of theoretical results.There has been considerable research interest in the ligand nature of N-heterocyclic carbenes (NHCs). In this work, two six-coordinate NHC iron porphyrin complexes [FeII(TTP)(1,3-Me2Imd)2] (TTP = tetratolylporphyrin, 1,3-Me2Imd = 1,3-dimethylimidazol-2-ylidene) and [FeIII(TDCPP)(1,3-Me2Imd)2]ClO4 (TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin) are reported. Single-crystal X-ray characterizations demonstrate that both complexes have strongly ruffled conformations and relatively perpendicular ligand orientations which are forced by the sterically bulky 1,3-Me2Imd NHC ligands. Multitemperature (4.2-300 K) and high magnetic field (0-9 T) Mössbauer and low-temperature (4.0 K) EPR spectroscopies definitely confirmed the low-spin states of [FeII(TTP)(1,3-Me2Imd)2] (S = 0) and [FeIII(TDCPP)(1,3-Me2Imd)2]ClO4 (S = 1/2). The similarity of 1,3-Me2Imd and imidazole, as well as the well-established correlations between the ligand nature and spectroscopic characteristics of [FeII,III(Porph)(L)2]0,+ (Porph porphyrin; L planar base ligand) species, allowed direct comparisons between the pair of ligands which revealed for the first time that NHC has a stronger π-acceptor ability than imidazoles, in addition to its very strong σ-donation.CREB (cyclic-AMP responsive element binding protein) binding protein (CBP) is a potential target for prostate cancer treatment. Herein, we report the structural optimization of a series of 1-(indolizin-3-yl)ethan-1-one compounds as new selective CBP bromodomain inhibitors, aiming to improve cellular potency and metabolic stability. This process led to compound 9g (Y08284), which possesses good liver microsomal stability and pharmacokinetic properties (F = 25.9%). Furthermore, the compound is able to inhibit CBP bromodomain as well as the proliferation, colony formation, and migration of prostate cancer cells. Additionally, the new inhibitor shows promising antitumor efficacy in a 22Rv1 xenograft model (TGI = 88%). This study provides new lead compounds for further development of drugs for the treatment of prostate cancer.We study the molecular properties of aqueous acetic acid and formic acid solutions with heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). For acid concentrations up to ∼5 M, we observe a strong increase of the responses of the acid hydroxyl and carbonyl stretch vibrations with increasing acid concentration due to an increase of the surface coverage by the acid molecules. At acid concentrations >5 M we observe first a saturation of these responses and then a decrease. For pure carboxylic acids we even observe a change of sign of the Im[χ(2)] response of the carbonyl vibration. The decrease of the response of the hydroxyl vibration and the decrease and sign change of the response of the carbonyl vibration indicate the formation of cyclic dimers, which only show a quadrupolar bulk response in the HD-VSFG spectrum because of their antiparallel conformation. We also find evidence for the presence of a quadrupolar response of the CH vibrations of the acid molecules.CO2 electroreduction (CO2RR) is a sustainable alternative for producing fuels and chemicals. Metal cations in the electrolyte have a strong impact on the reaction, but mainly alkali species have been studied in detail. In this work, we elucidate how multivalent cations (Li+, Cs+, Be2+, Mg2+, Ca2+, Ba2+, Al3+, Nd3+, and Ce3+) affect CO2RR and the competing hydrogen evolution by studying these reactions on polycrystalline gold at pH = 3. We observe that cations have no effect on proton reduction at low overpotentials, but at alkaline surface pH acidic cations undergo hydrolysis, generating a second proton reduction regime. The activity and onset for the water reduction reaction correlate with cation acidity, with weakly hydrated trivalent species leading to the highest activity. Acidic cations only favor CO2RR at low overpotentials and in acidic media. At high overpotentials, the activity for CO increases in the order Ca2+ less then Li+ less then Ba2+ less then Cs+. To favor this reaction there must be an interplay between cation stabilization of the *CO2- intermediate, cation accumulation at the outer Helmholtz plane (OHP), and activity for water reduction. Ab initio molecular dynamics simulations with explicit electric field show that nonacidic cations show lower repulsion at the interface, accumulating more at the OHP, thus triggering local promoting effects. Water dissociation kinetics is increasingly promoted by strongly acidic cations (Nd3+, Al3+), in agreement with experimental evidence. Cs+, Ba2+, and Nd3+ coordinate to adsorbed CO2 steadily; thus they enable *CO2- stabilization and barrierless protonation to COOH and further reduction products.