Haysrye3029

The molecular structure of nanothreads produced by the slow compression of 13C4-furan was studied by advanced solid-state NMR. Spectral editing showed that >95% of carbon atoms were bonded to one hydrogen (C-H) and that there were 2-4% CH2, 0.6% C═O, and less then 0.3% CH3 groups. Alkenes accounted for 18% of the CH moieties, while trapped, unreacted furan made up 7%. Two-dimensional (2D) 13C-13C and 1H-13C NMR identified 12% of all carbon in asymmetric O-CH═CH-CH-CH- and 24% in symmetric O-CH-CH═CH-CH- rings. While the former represented defects or chain ends, some of the latter appeared to form repeating thread segments. Around 10% of carbon atoms were found in highly ordered, fully saturated nanothread segments. Unusually slow 13C spin-exchange with sites outside the perfect thread segments documented a length of at least 14 bonds; the small width of the perfect-thread signals also implied a fairly long, regular structure. Carbons in the perfect threads underwent relatively slow spin-lattice relaxation, indicating slow spin exchange with other threads and smaller amplitude motions. Through partial inversion recovery, the signals of the perfect threads were observed and analyzed selectively. Previously considered syn-threads with four different C-H bond orientations were ruled out by centerband-only detection of exchange NMR, which was, on the contrary, consistent with anti-threads. The observed 13C chemical shifts were matched well by quantum-chemical calculations for anti-threads but not for more complex structures like syn/anti-threads. These observations represent the first direct determination of the atomic-level structure of fully saturated nanothreads.In the search for potential new metal-based antitumor agents, two series of nonclassical palladium(II) pincer complexes based on functionalized amides with S-modified cysteine and homocysteine residues have been prepared and fully characterized by 1D and 2D NMR (1H, 13C, COSY, HMQC or HSQC, 1H-13C, and 1H-15N HMBC) and IR spectroscopy and, in some cases, X-ray diffraction. Most of the resulting complexes exhibit a high level of cytotoxic activity against several human cancer cell lines, including colon (HCT116), breast (MCF7), and prostate (PC3) cancers. Some of the compounds under consideration are also efficient in both native and doxorubicin-resistant transformed breast cells HBL100, suggesting the prospects for the creation of therapeutic agents based on the related compounds that would be able to overcome drug resistance. An analysis of different aspects of their biological effects on living cells has revealed a remarkable ability of the S-modified derivatives to induce cell apoptosis and efficient cellular uptake of their fluorescein-conjugated counterpart, confirming the high anticancer potential of Pd(II) pincer complexes derived from functionalized amides with S-donor amino acid pendant arms.Organic-inorganic hybrid metal halides have attracted widespread attention as emerging optoelectronic materials, especially in solid-state lighting, where they can be used as single-component white-light phosphors for white light-emitting diodes. Herein, we have successfully synthesized a zero-dimensional (0D) organic-inorganic hybrid mixed-metal halide (Bmpip)2PbxSn1-xBr4 (0 less then x less then 1, Bmpip+ = 1-butyl-1-methyl-piperidinium, C10H22N+) that crystallizes in a monoclinic system in the C2/c space group. Pb2+ and Sn2+ form a four-coordinate seesaw structure separated by organic cations forming a 0D structure. For different excitation wavelengths, (Bmpip)2PbxSn1-xBr4 (0 less then x less then 1) exhibits double-peaked emission at 470 and 670 nm. The emission color of (Bmpip)2PbxSn1-xBr4 can be easily tuned from orange-red to blue by adjusting the Pb/Sn molar ratio or excitation wavelength. Representatively, (Bmpip)2Pb0.16Sn0.84Br4 exhibits approximately white-light emission with high photoluminescence quantum yield up to 39%. Interestingly, the color of (Bmpip)2PbxSn1-xBr4 can also be easily tuned by temperature, promising its potential for application in temperature measurement and indication. Phosphor-converted light-emitting diodes are fabricated by combining (Bmpip)2PbxSn1-xBr4 and 365 nm near-UV LED chips and exhibit high-quality light output.Aqueous binary colloids of niobate and clay nanosheets, prepared by the exfoliation of their mother layered crystals, are unique colloidal systems characterized by the separation of niobate and clay nanosheet phases, where niobate nanosheets form liquid crystalline domains with the size of several tens of micrometers among isotropically dispersed clay nanosheets. The binary colloids show unusual photocatalytic reactions because of the spatial separation of photocatalytically active niobate and photochemically inert clay nanosheets. The present study shows structural conversion of the binary colloids with an external electric field, resulting in the onsite alignment of colloidal nanosheets to improve the photocatalytic performance of the system. The colloidal structure is reshaped by the growth of liquid crystalline domains of photocatalytic niobate nanosheets and by their electric alignment. Niobate nanosheets are assembled by the domain growth process and then aligned by AC voltage, although clay nanosheets do not respond to the electric field. Photocatalytic decomposition of the cationic rhodamine 6G dye, which is selectively adsorbed on clay nanosheets, is examined for the niobate-clay binary nanosheet colloids with or without domain growth and electric field. The fastest decomposition is observed for the electrically aligned colloid without the domain growth, whereas the sample with the domain growth and without the electric alignment shows the slowest decomposition. The results demonstrate the improvement of the photocatalytic performance by changing the colloidal structure, even though the sample composition is the same.The Fenton reaction is considered to be of great significance in the initial attack of lignocellulose in wood-decaying fungi. Quinone redox cycling is the main way to induce the Fenton reaction in fungi. We show that lytic polysaccharide monooxygenases (LPMOs), through LPMO-catalyzed oxidation of hydroquinone, can efficiently cooperate with glucose dehydrogenase (GDH) to achieve quinone redox cycling. The LPMO/GDH system can enhance Fe3+-reducing activity, H2O2 production, and hydroxyl radical generation, resulting in a fueled Fenton reaction. The system-generated hydroxyl radicals exhibited a strong capacity to decolorize different synthetic dyes and degrade lignin. Our results reveal a potentially critical connection between LPMOs and the Fenton reaction, suggesting that LPMOs could be involved in xenobiotic compound and lignin degradation in fungi. This new role of LPMOs may be exploited for application in biorefineries.Two paralogs of the guanine dissociation inhibitor-like solubilizing factors UNC119, UNC119A and UNC119B, are present in the human genome. UNC119 binds to N-myristoylated proteins and masks the hydrophobic lipid from the hydrophilic cytosol, facilitating trafficking between different membranes. Two classes of UNC119 cargo proteins have been classified low affinity cargoes, released by the Arf-like proteins ARL2 and ARL3, and high affinity cargoes, which are specifically released by ARL3 and trafficked to either the primary cilium or the immunological synapse. The UNC119 homologues have reported differences in functionality, but the structural and biochemical bases for these differences are unknown. Using myristoylated peptide binding and release assays, we show that peptides sharing the previously identified UNC119A high affinity motif show significant variations of binding affinities to UNC119B of up to 427-fold. Furthermore, we solve the first two crystal structures of UNC119B, one in complex with the high affinity cargo peptide of LCK and a second one in complex with the release factor ARL3. Using these novel structures, we identify a stretch of negatively charged amino acids unique to UNC119B that may undergo a conformational change following binding of a release factor which we propose as an additional release mechanism specific to UNC119B.Mechanical stability and multicycle durability are essential for emerging solid sorbents to maintain an efficient CO2 adsorption capacity and reduce cost. In this work, a strong foam-like composite is developed as a CO2 sorbent by the in situ growth of thermally stable and microporous metal-organic frameworks (MOFs) in a mesoporous cellulose template derived from balsa wood, which is delignified by using sodium chlorite and further functionalized by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation. The surface carboxyl groups in the TEMPO-oxidized wood template (TO-wood) facilitate the coordination of the cellulose network with multivalent metal ions and thus enable the nucleation and in situ growth of MOFs including copper benzene-1,3,5-tricarboxylate [Cu3(BTC)2], zinc 2-methylimidazolate, and aluminum benzene-1,3,5-tricarboxylate. The TO-wood/Cu3(BTC)2 composite shows a high specific surface area of 471 m2 g-1 and a high CO2 adsorption capacity of 1.46 mmol g-1 at 25 °C and atmospheric pressure. It also demonstrates high durability during the temperature swing cyclic CO2 adsorption/desorption test. In addition, the TO-wood/Cu3(BTC)2 composite is lightweight but exceptionally strong with a specific elastic modulus of 3034 kN m kg-1 and a specific yield strength of 68 kN m kg-1 under the compression test. The strong and durable TO-wood/MOF composites can potentially be used as a solid sorbent for CO2 capture, and their application can possibly be extended to environmental remediation, gas separation and purification, insulation, and catalysis.Here, we investigate competitive adsorption and photocatalytic reaction over TiO2@SiO2 NO conversion efficiency decreases by 29.1%, and the adsorption capacity decreases from 0.125 to 0.095 mmol/g due to the influence of SO2. According to identification and comparative analysis of the IR signal, SO2 has little effect on the NO conversion route and intermediates (adsorbed NO → nitrite → nitrate), but accelerates the deactivation of catalysts. The electronic interaction scheme from density functional theory (DFT) confirms that surface hydroxyls create an unsaturated coordination of neighboring Ti or O atoms, which is favorable for NO/SO2 adsorption on anatase (101). In addition, the lone pair electrons of N or S atoms prefer to be delocalized and form covalent bonds with active surface-O on the (101) facet with terminal hydroxyls. However, preadsorbed SO2 could offset the increase of hydroxyls and strongly inhibit NO adsorption, which is consistent with the result performance evaluation. A possible reaction mechanism characterized by oxygen vacancies and·O2- is proposed, while the essential reason of catalyst deactivation and regeneration is theoretically analyzed based on the experimental and DFT calculation.Mitochondrial drug delivery has attracted increasing attention in various mitochondrial dysfunction-associated disorders such as cancer owing to the important role of energy production. Herein, we report a lysosomal pH-activated mitochondrial-targeting polymer nanoparticle to overcome drug resistance by a synergy between mitochondrial delivery of doxorubicin (DOX, an anticancer drug) and erlotinib-mediated inhibition of drug efflux. The obtained nanoparticles, DE-NPs could maintain negative charge and have long blood circulation while undergoing charge reversal at lysosomal pH after internalization by cancer cells. Thereafter, the acidity-activated polycationic and hydrophobic polypeptide domains boost lysosomal escape and mitochondrial-targeting drug delivery, leading to mitochondrial dysfunction, ATP suppression, and cell apoptosis. click here Moreover, the suppressed ATP supply and erlotinib enabled dual inhibition of drug efflux by DOX-resistant MCF-7/ADR cells, leading to significantly augmented intracellular DOX accumulation and a synergistic anticancer effect with a 17-fold decrease of IC50 relative to DOX.