Jantzenbrowne7491

Thus, both debromination and chlorine-bromine exchange may be important reactions during the thermal processing of e-waste. The results on mixed chlorinated/brominated TBBPA transformation products provided new insights into TBBPA transformation. The elevated levels of the transformation products of TBBPA suggested that these products should be targeted to avoid underestimation of possible health risks.Deoxygenative radical C-C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report a direct dehydroxylative radical alkylation reaction of tertiary alcohols. This new protocol shows the feasibility of generating tertiary carbon radicals from alcohols and offers an approach for the facile and precise construction of all-carbon quaternary centers. The reaction proceeds with a broad substrate scope of alcohols and activated alkenes. It can tolerate a wide range of electrophilic coupling partners, including allylic carboxylates, aryl and vinyl electrophiles, and primary alkyl chlorides/bromides, making the method complementary to the cross-coupling procedures. The method is highly selective for the alkylation of tertiary alcohols, leaving secondary/primary alcohols (benzyl alcohols included) and phenols intact. The synthetic utility of the method is highlighted by its 10-g-scale reaction and the late-stage modification of complex molecules. A combination of experiments and density functional theory calculations establishes a plausible mechanism implicating a tertiary carbon radical generated via Ti-catalyzed homolysis of the C-OH bond.Black carbon (BC) aerosols perturb climate and impoverish air quality/human health-affecting ∼1.5 billion people in South Asia. However, the lack of source-diagnostic observations of BC is hindering the evaluation of uncertain bottom-up emission inventories (EIs) and thereby also models/policies. Here, we present dual-isotope-based (Δ14C/δ13C) fingerprinting of wintertime BC at two receptor sites of the continental outflow. Our results show a remarkable similarity in contributions of biomass and fossil combustion, both from the site capturing the highly populated highly polluted Indo-Gangetic Plain footprint (IGP; Δ14C-fbiomass = 50 ± 3%) and the second site in the N. Indian Ocean representing a wider South Asian footprint (52 ± 6%). Yet, both sites reflect distinct δ13C-fingerprints, indicating a distinguishable contribution of C4-biomass burning from peninsular India (PI). Tailored-model-predicted season-averaged BC concentrations (700 ± 440 ng m-3) match observations (740 ± 250 ng m-3), however, unveiling a systematically increasing model-observation bias (+19% to -53%) through winter. Inclusion of BC from open burning alone does not reconcile predictions (fbiomass = 44 ± 8%) with observations. Direct source-segregated comparison reveals regional offsets in anthropogenic emission fluxes in EIs, overestimated fossil-BC in the IGP, and underestimated biomass-BC in PI, which contributes to the model-observation bias. This ground-truthing pinpoints uncertainties in BC emission sources, which benefit both climate/air-quality modeling and mitigation policies in South Asia.Sorption of nutrients such as phosphate (P) and silicate (Si) by ferric iron (oxyhydr)oxides (FeOx) modulates nutrient mobility and alters the structure and reactivity of the FeOx. We investigated the impact of these interactions on FeOx transformations using a novel approach with samplers containing synthetic FeOx embedded in diffusive hydrogels. The FeOx were prepared by Fe(III) hydrolysis and Fe(II) oxidation, in the absence and presence of P or Si. Coprecipitation of P or Si during synthesis altered the structure of Fe precipitates and, in the case of Fe(II) oxidation, lepidocrocite was (partly) substituted by poorly ordered FeOx. The pure and P- or Si-bearing FeOx were deployed in (i) freshwater sediment rich in dissolved Fe(II) and P and (ii) marine sediment with sulfidic pore water. Iron(II)-catalyzed crystallization of poorly ordered FeOx was negligible, likely due to surface passivation by adsorption of dissolved P. Reaction with dissolved sulfide was modulated by diffusion limitations and therefore the extent of sulfidation was the lowest for poorly ordered FeOx with high reactivity toward sulfide that created temporary, local sulfide depletion (Fh less then Lp). We show that coprecipitation-induced changes in the FeOx structure affect coupled iron-nutrient cycling in aquatic ecosystems. The gel-based method enriches our geochemical toolbox by enabling detailed characterization of target phases under natural conditions.Nonlinear-optical (NLO) crystals, which can regulate the laser wavelength through a cascading second-harmonic-generation technique, have been widely utilized in the field of optoelectronics. In this work, we grew the NLO borate crystal Rb3YB6O12 (RYBO) using the spontaneous crystallization method. RYBO crystallizes in a chiral trigonal space group of R32 with a new type of structural arrangement built from Y-O short chains and B5O10 groups. It is significantly different from the known structure of chemical analogues Rb3REB6O12 (RE = Nd, Eu) not only in the halved unit cell parameter but also in the Y-O connection manner. The NLO response of RYBO is about 0.8KDP, 8-fold larger than that of KB5O8·4H2O with the same B5O10 groups because of the coexistence of two NLO-active units of the distorted YO6 octahedra and B5O10 anions. Thanks to the short ultraviolet (UV) cutoff, RYBO may have potential NLO applications in the UV and even deep-UV spectral regions.Natural selection has endorsed proteins with amazing structures and functionalities that cannot be matched by synthetic means, explaining the exponential interest in developing protein-based materials. Triciribine mouse Protein self-assembly allows fabricating complex supramolecular structures from relatively simple building blocks, a bottom-up strategy naturally employed by amyloid fibrils. However, the design of amyloid-inspired materials with biological activity is inherently difficult. Here, we exploit a modular procedure to generate functional amyloid nanostructures with tight control of their mesoscopic properties. The soft amyloid core of a yeast prion was fused to dihydrofolate reductase through flexible linkers of different sizes. This enabled us to produce, for the first time, biocompatible protein-only amyloid-like oligomeric nanoparticles with defined dimensions in which the embedded enzyme remained highly active, as assessed by biophysical and enzymatic assays. The modular design allowed one to obtain multifunctional nanoparticles by incorporating the antibody-binding Z-domain to the protein fusion.