Adlerburnette2660

An organometallic complex that mimics an amino acid, also known as an amino acid isostere, can be synthesized from a functionalized bipyridine ligand and a fac-[Re(CO)3]+ center. The reaction of an achiral ligand and metal results in a racemic mixture of chiral-at-metal complexes. These metal species have amine and carboxy termini, a side chain type unit that can be varied, as well as the chiral metal that is analogous to the α carbon of an amino acid. The racemic mixtures can be separated into enantiomers by chiral chromatography, and the metal complexes can be incorporated into peptides by using solid-phase peptide synthesis.Photocatalytic materials are proved to effectively eliminate gaseous pollutants and are widely used in the environment. However, as one of the rare experiments focusing on their influence on secondary aerosol formation generated in the gas phase (SAg), our study demonstrated the high-yield SAg formation in the photocatalysis process. In this study, the photodegradation of SO2 by TiO2 under various relative humidity (RH) conditions was deeply explored with multiple methods. Unexpectedly, H2SO4 aerosols (SAg-H2SO4) in yields of 10.10-32.64% were observed under the studied RH conditions for the first time. Gaseous •OH and H2O2 generated from the oxidation of H2O and reduction of O2 by TiO2 were directly detected in the photocatalysis process, and they were identified as the determining factor for SAg-H2SO4 formation. The formation of SAg-H2SO4 was also influenced by RH, the heterogeneous reaction of SO2, and the uptake of H2SO4. The role of the released gaseous •OH and H2O2 on atmospheric chemistry was proved to be unignorable by adopting the obtained parameters into the real environment. These findings provided direct experimental evidence of secondary pollution in the photocatalysis process and are of great significance to the field of atmospheric environment and photocatalytic materials.Analysis of subpercent local strain is important for a deeper understanding of nanomaterials, whose properties often depend on the strain. Conventional strain analysis has been performed by measuring interatomic distances from scanning transmission electron microscopy (STEM) images. However, measuring subpercent strain remains a challenge because the peak positions in STEM images do not precisely correspond to the real atomic positions due to disturbing influences, such as random noise and image distortion. Here, we utilized an advanced data-driven analysis method, Gaussian process regression, to predict the true strain distribution by reconstructing the true atomic positions. As a result, a precision of 0.2% was achieved in strain measurement at the atomic scale. The method was applied to gold nanoparticles of different shapes to reveal the shape dependence of the strain distribution. A spherical gold nanoparticle showed a symmetric strain distribution with a contraction of ∼1% near the surface owing to surface relaxation. By contrast, a gold nanorod, which is a cylinder terminated by hemispherical caps on both sides, showed nonuniform strain distributions with lattice expansions of ∼0.5% along the longitudinal axis around the caps except for the contraction at the surface. Our results indicate that the strain distribution depends on the shape of the nanomaterials. The proposed data-driven analysis is a convenient and powerful tool to measure the strain distribution with high precision at the atomic scale.The dissolution of transition metals (TMs) from cathode materials and their deposition on the anode represents a serious degradation process and, with that, a shortcoming of lithium-ion batteries. It occurs particularly at high charge voltages (>4.3 V), contributing to severe capacity loss and thus impeding the increase of cell voltage as a simple measure to increase energy density. We present here for the first time the online detection of dissolved TMs from a Ni-rich layered oxide cathode material with unprecedented potential and time resolution in potentiodynamic scans. To this aid, we used the coupling of an electroanalytical flow cell (EFC) with inductively coupled plasma mass spectrometry (ICP-MS), which is demonstrated to be an ideal tool for a fast performance assessment of new cathode materials from initial cycles. The simultaneous analysis of electrochemical and dissolution data allows hitherto hidden insights into the processes' characteristics and underlying mechanisms.Recent progress in the development of photocatalytic reactions promoted by visible light is leading to a renaissance in the use of photochemistry in the construction of structurally elaborate organic molecules. Because of the rich functionality found in natural products, studies in natural product total synthesis provide useful insights into functional group compatibility of these new photocatalytic methods as well as their impact on synthetic strategy. In this review, we examine total syntheses published through the end of 2020 that employ a visible-light photoredox catalytic step. To assist someone interested in employing the photocatalytic steps discussed, the review is organized largely by the nature of the bond formed in the photocatalytic step.DNAzymes with enzymatic activity identified from random DNA pools by in vitro selection have recently attracted considerable attention. In this work, a DNAzyme-based autonomous-motion (AM) molecular machine is demonstrated for sensitive simultaneous imaging of different intracellular microRNAs (miRNAs). The AM molecular machine consists of two basic elements, one of which is a target-analogue-embedded double-stem hairpin substrate (TDHS) and the other is a locking-strand-silenced DNAzyme (LSDz). LSDz can be activated by target miRNA and catalytically cleave TDHS, generating Clv-TDHS and releasing free target analogue capable of triggering the next round of cleavage reaction. As such, the molecular machine can exert sustainable autonomous operation, producing an enhanced signal. Because the active target analogue comes from the machine itself and offers cyclical stimulation in a feedback manner, this target-induced autonomous cleavage circuit is termed a self-feedback circuit (SFC). The SFC-based molecular machine can be used to quantify miRNA-21 down to 10 pM without interference from nontarget miRNAs, indicating a substantial improvement in assay performance compared with its counterpart system without an SFC effect. Moreover, due to the enzyme-free process, the AM molecular machine is suitable for miRNA imaging in living cells, and the quantitative results are consistent with the gold standard PCR assay. More interestingly, the AM molecular machine can be used for the simultaneous fluorescence imaging of several intracellular miRNAs, enabling the accurate discrimination of cancerous cells (e.g., HeLa and MCF-7) from healthy cells. The SFC-based autonomous-motion machine is expected to be a promising tool for the research of molecular biology and early diagnosis of human diseases.As molecular computing materials, information-encoded deoxyribonucleic acid (DNA) strands provide a logical computing process by cascaded and parallel chain reactions. However, the reactions in DNA-based combinational logic computing are mostly achieved through a manual process by adding desired DNA molecules in a single microtube or a substrate. For DNA-based Boolean logic, using microfluidic chips can afford automated operation, programmable control, and seamless combinational logic operation, similar to electronic microprocessors. In this paper, we present a programmable DNA-based microfluidic processing unit (MPU) chip that can be controlled via a personal computer for performing DNA calculations. To fabricate this DNA-based MPU, polydimethylsiloxane was cast using double-sided molding techniques for alignment between the microfluidics and valve switch. For a uniform surface, molds fabricated using a three-dimensional printer were spin-coated by a polymer. For programming control, the valve switch arms were operated by servo motors. In the MPU controlled via a personal computer or smartphone application, the molecules with two input DNAs and a logic template DNA were reacted for the basic AND and OR operations. Furthermore, the DNA molecules reacted in a cascading manner for combinational AND and OR operations. Finally, we demonstrated a 2-to-1 multiplexer and the XOR operation with a three-step cascade reaction using the simple DNA-based MPU, which can perform Boolean logic operations (AND, OR, and NOT). SAR 245509 Through logic combination, this DNA-based Boolean logic MPU, which can be operated using programming language, is expected to facilitate the development of complex functional circuits such as arithmetic logical units and neuromorphic circuits.ConspectusNanoparticles are widely used in various biomedical applications as drug delivery carriers, imaging probes, single-molecule tracking/detection probes, artificial chaperones for inhibiting protein aggregation, and photodynamic therapy materials. One key parameter of these applications is the ability of the nanoparticles to enter into the cell cytoplasm, target different subcellular compartments, and control intracellular processes. This is particularly the case because nanoparticles are designed to interact with subcellular components for the required biomedical performance. However, cells are protected from their surroundings by the cell membrane, which exerts strict control over entry of foreign materials. Thus, nanoparticles need to be designed appropriately so that they can readily cross the cell membrane, target subcellular compartments, and control intracellular processes.In the past few decades there have been great advancements in understanding the principles of cellular uptake of foreign matConclusions and Outlook where we discuss a vision for the development of subcellular targeting nanodrugs and imaging nanoprobes by adapting to these surface chemistry principles.A zinc-based metal organic framework, Zn-MOF-74, which has a unique one-dimensional (1D) channel and nanoscale aperture size, was rapidly obtained in 10 min using a de novo mild water-based system at room temperature, which is an example of green and sustainable chemistry. First, catalase (CAT) enzyme was encapsulated into Zn-MOF-74 (denoted as CAT@Zn-MOF-74), and comparative assays of biocatalysis, size-selective protection, and framework-confined effects were investigated. Electron microscopy and powder X-ray diffraction were used for characterization, while electrophoresis and confocal microscopy confirmed the immobilization of CAT molecules inside the single hexagonal MOF crystals at loading of ∼15 wt %. Furthermore, the CAT@Zn-MOF-74 hybrid was exposed to a denaturing reagent (urea) and proteolytic conditions (proteinase K) to evaluate its efficacy. The encapsulated CAT maintained its catalytic activity in the decomposition of hydrogen peroxide (H2O2), even when exposed to 0.05 M urea and proteinase K, yzyme encapsulation in MOFs, which may help to meet the increasing demand for their industrial applications.It remains challenging to promptly inhibit and autonomically heal electrical trees inside insulating dielectrics, which are caused by sustained strong electrical fields and substantially shorten electronic device lifetimes and even cause premature failure of electrical equipment. Therefore, we demonstrate a magnetically targeted ultraviolet (UV)-induced polymerization functional microcapsule (MTUF-MC) to endow insulating materials with physical and electrical dual-damage self-healing capabilities. Specifically, Fe3O4@SiO2 and TiO2 nanoparticles, which serve as magnetic targets and UV shields (thereby preventing the healing agent from prematurely triggering), constitute a functional microcapsule shell, ensuring a low dopant concentration and excellent self-healing ability of the epoxy composites without affecting the intrinsic performance of the matrix. By exploiting in situ electroluminescence originating from electrical trees, UV-induced polymerization of healing agent is handily triggered without any applying external stimuli to intelligently, contactlessly, and autonomously self-healing electrical trees inside insulating dielectrics.