Meinckebray5310

We report a photosensitive polymyxin B-modified conjugated oligomer nanoparticle that integrates the targeted identification and synergistic photodynamic therapy in one treatment against resistant Gram-negative bacteria. The study expands the application of antibiotics and opens a new avenue for enhancing photodynamic antimicrobial therapy and fighting bacterial resistance.The twisted intramolecular charge transfer (TICT) mechanism has guided the development of numerous bright and sensitive fluorophores. This review briefly overviews the history of establishing the TICT mechanism, and systematically summarizes the molecular design strategies in modulating the TICT tendency of various organic fluorophores towards different applications, along with key milestone studies and representative examples. Additionally, we also succinctly review the twisted intramolecular charge shuttle (TICS) and twists during photoinduced electron transfer (PET), and compare their similarities and differences with TICT, with emphasis on understanding the structure-property relationships between the twisted geometries and how they can directly affect the fluorescence of the molecules. Such structure-property relationships presented herein will greatly aid the rational development of fluorophores that involve molecular twisting in the excited state.A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the trans-4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics. Time constants for the initial to the intermediate and hot product and to the final product are obtained. The acceleration of the dynamics by methyl substitution and the strong contribution of intracluster vibrational energy redistribution in the termination of the solvation dynamics is suggested. This picture is well confirmed by the ab initio on-the-fly molecular dynamics simulations. Vibrational assignments of 4MetFA and 4MetFA-W in the neutral (S0 and S1) and ionic (D0) electronic states measured by ns IR dip and electron-impact IR photodissociation spectroscopy are also discussed prior to the results of time-resolved spectroscopy.Due to the limitation of technology, electronic computing is approaching the limit of technology, and new computing tools need to be developed. Here, we build a three-input cascade logic gate based on the advantages of biomolecules, particularly DNA, in the construction of computational logic systems, combined with metal ions and graphene oxide (GO). It is worth mentioning that this study uses a variety of research methods. In addition to the commonly used biological experiments, NUPACK and visual DSD simulation methods are used for analysis, and orthogonal, standardized and other statistical means are used to simplify the experimental process and make the results intuitive. Finally, the designed three-input logic gate is successfully constructed, and it is found that it may have the potential to realize complex computing.An SPA-triazolium bromide-catalyzed transannular C-acylation of enol lactones is presented. This methodology provides convenient access to a range of enantioenriched spirocyclic 1,3-diketones in moderate to high yields and enantioselectivities and features a broad substrate scope in terms of enol lactones. The catalytic capability of this triazolium salt catalyst is also demonstrated in this enantioselective transformation, which could inspire its further application.Microporous organic polymers (MOPs) are a new class of microporous materials. Due to their high porosity, large pore volume, and large surface area, MOPs exhibit excellent performance in gas adsorption and storage, membrane separation, ion capture, heterogeneous catalysis, light energy conversion and storage, capacitance, and other fields. However, selecting high-performance materials for specific applications from thousands of candidate MOPs is a key problem. Traditional design strategies for new materials with targeted properties, including trial-and-error and relying on the experiences of domain experts, are time- and cost-consuming. With the rapid development of computation technology and theoretical chemistry, the discovery of new materials is no longer a purely experimental subject. Breaking away from the traditional trial-and-error strategy for materials discovery, materials design is emerging and gaining increasing attention. In addition, the ability to collect "big data" has greatly improved and has further stimulated the development of new methods for materials design and discovery. In this perspective, we examine how data-driven techniques combine artificial intelligence (AI) and human expertise, playing a significant role in the design of MOPs. Such analytics can significantly reduce time-to-insight and accelerate the cost-effective materials discovery, which is the goal for designing future MOPs.Localised singlet cyclopentane-1,3-diyl diradicaloids have been considered promising candidates for constructing carbon-carbon π-single bonds (C-π-C). However, the high reactivity during formation of the σ-bond has limited a deeper investigation of its unique chemical properties. In this feature article, recent progress in kinetic stabilisation based on the "stretch effect" and the "solvent dynamic effect" induced by the macrocyclic system is summarised. Singlet diradicaloids S-DR4a/b and S-DR4d containing macrocyclic rings showed much longer lifetimes at 293 K (14 μs for S-DR4a and 156 μs for S-DR4b in benzene) compared to the parent singlet diradicaloid S-DR2 having no macrocyclic ring (209 ns in benzene). Furthermore, the dynamic solvent effect in viscous solvents was observed for the first time in intramolecular σ-bond formation, the lifetime of S-DR4d increased to 400 μs in the viscous solvent glycerin triacetin at 293 K. The experimental results proved the validity of the "stretch effect" and the "solvent dynamic effect" on the kinetic stabilisation of singlet cyclopentane-1,3-diyl diradicaloids, and provided a strategy for isolating the carbon-carbon π-single bonded species (C-π-C), and towards a deeper understanding of the nature of chemical bonding.The electrolysis of water using renewable energy is a promising approach to developing a sustainable hydrogen-based economy. To improve the efficiency of this process, it will be necessary to develop highly active electrocatalysts that promote the oxygen evolution reaction (OER). In the present study, the OER activity of a nickel oxide electrocatalyst was dramatically improved following the addition of a diamine to the electrolyte solution during electrodeposition. Operando UV/vis absorption spectroscopy was used to assess a number of nickel catalysts containing various diamines and other organic compounds. The data indicate that Ni(II) complexes were formed with the diamines during electrodeposition. Consequently, the catalytic activity of these materials was enhanced based on increased concentrations of active reaction sites for the OER process. Ni K-edge X-ray absorption spectra showed that these catalysts were composed of γ-NiOOH with a Ni3.6+ valence state. The coordination of the diamine molecules to the γ-NiOOH produced structural distortion that contributed to improved OER activity. This structural distortion is likely the most important factor in enhancing the OER activity of inorganic-organic composite catalysts.A multidisciplinary study is presented to shed light on how pyrylium frameworks, as π-hole donors, establish π-π interactions. The combination of CSD analysis, computational modelling (ab intitio, DFT and MD simulations) and experimental NMR spectroscopy data provides essential information on the key parameters that characterize these intereactions, opening new avenues for further applications of this versatile heterocycle.The lowest-energy structures of AgCu nanoalloys are searched for by global optimization algorithms for sizes 100 and 200 atoms depending on composition. Even though the AgCu system is very weakly miscible in macroscopic samples, the mixing energy for these nanoalloys turns out to be clearly negative for both sizes, a result which is attributed to the stabilization of non-crystalline Cu@Ag core-shell structures at the nanoscale. The mixing energy is a quantity nowadays unknown in its functional form, so that its prediction may take advantage of machine learning techniques. A support vector regressor is then implemented to successfully predict the mixing energy of AgCu nanoalloys of both sizes. Moreover, with the help of unsupervised learning algorithms, it is shown that the automatic classification of such nanoalloys into different physically meaningful structural families is indeed possible. Finally, thanks to the harmonic superposition approximation, the temperature-dependent probabilities of such structural families are calculated.NC@Co-HPNC is synthesized, which exhibits a superior ORR/OER performance in acid/base solution. Hence, acid-base dual-electrolyte-based Zn-air batteries using NC@Co-HPNC reveal a long cycling life and a super-high voltage (2.1 V).The reductive cross-coupling of terminal alkenes and N-heterocyclic bromides has been demonstrated by ligand optimization of Pd and CuH catalysis. The optimized ligands are Briphos, a π-acceptor monodentate phosphorus ligand, for Pd catalysis and DTB-DPPBz, a sterically bulky bidentate phosphorus ligand, for CuH catalysis. These conditions were further applied to the gram-scale production of clathryimine B.We describe a novel mechanism of stabilization of the E-ac isomer of an arylhydrazide via nN → π*Ar interactions. Rapamycin purchase We further show that when a leaving group (F) is present at the ortho-position of the carbonyl group of such an arylhydrazide, the nN → π*Ar interaction facilitates an SNAr autocyclization reaction to produce indazolone, an important heterocycle with biological activity. Faster autocyclization of arylhydrazide is observed when an electron withdrawing group is present in the aryl ring, which is a characteristic of SNAr reactions.In this work, organic supramolecular linkers involving cucubit[6]urils CB[6] and N,N'-hexamethylene-bis(pyrazinyl hexafluorophosphate) (BPHF@CB[6]) were utilized to assemble dodenuclear silver chalcogenolate clusters into three one-dimensional (1D) materials under different synthesis conditions. These three crystal structures of CB[6]-based sliver cluster-organic rotaxane frameworks were well resolved, and their emission properties were investigated systematically. This construction strategy involving organic supramolecular linkers gives a new methodology for cluster-assembled materials with intriguing structural and functional properties.In periodic W/Be multilayers, thickness-dependent microstructural and phase modifications were investigated in W and Be layers. In X-ray diffraction, α-W was predominant for the ultrathin layer of W, while β-W evolved along with the α-W phase for higher film thickness. For the thicker layers, the thermodynamically metastable β-W vanished and a single well-defined preferably oriented stable α-W phase was observed. The lattice spacing revealed that these phases exist in the tensile stressed condition. With the increase in thickness of Be layers, the blueshift and narrow linewidth of the transverse optical (TO) phonon mode was observed in Raman scattering studies. However, the TO mode was redshifted and the linewidth was further narrowed consistently with an increase in the thermal annealing temperature of the multilayers. The investigation has quantified an increase in compressive strain and reduction of defects with an increase in thickness of the Be layers. However, for thermally annealed samples, the compressive strain in the Be layers was relaxed and crystalline quality was improved.