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This study aims to identify the kinetic features of individual reaction steps of the multistep thermal dehydration of calcium sulfate dihydrate (CS-DH) to anhydride via a hemihydrate (CS-HH) intermediate by achieving the universal kinetic description of each reaction step under different heating and water vapor pressure (p(H2O)) conditions. The mass loss processes of the thermal dehydration of CS-DH were systematically traced via humidity-controlled thermogravimetry under isothermal and linear nonisothermal conditions at various atmospheric p(H2O) values. After reconfirming the variation in the thermal dehydration pathway from a single-step dehydration to anhydride to a multistep process via the CS-HH intermediate with an increase in the p(H2O) value, the kinetic curves for each component reaction step were obtained by separating each component process from the partially overlapping mass-loss curves by kinetic deconvolution analysis as required. The induction period (IP) and the mass-loss processes of the thermal dehydrations of CS-DH to anhydride and CS-HH intermediate were compared, wherein more significant retardation effects of water vapor were observed for the IP process followed by direct dehydration to anhydride and for the mass-loss process from CS-DH to the CS-HH intermediate. The universal kinetic behavior of the thermal dehydration of the CS-HH intermediate to anhydride was compared with that of the CS-HH reagent; thus, comparable universal kinetic behaviors were observed except the reaction geometry. Based on the universal kinetic results, the key kinetic phenomenon for regulating the variation of the thermal dehydration pathway of CS-DH was discussed.External light-independent antitumor PDT is successfully realized with a covalent organic framework (COF)-based host-guest nanosystem. Its highly effective antitumor behavior is fully demonstrated by both H2O2-overexpressed 4T1 and H2O2-less expressed HCT116 and MCF-7 xenograft models.A CO probe with PEGylation is synthesized, achieving the detection of CO in pure water solution with high intensity color change and fluorescence enhancement. Importantly, this probe with high affinity to paper strips and low toxicity to living cells is successfully used for sensing CO in air and in living cells.Enantiomorphic right- and left-handed polyproline type I helices in four cyclic dodecapeptoids with methoxyethyl and propargyl side chains are observed for the first time by single crystal X-ray diffraction. The peculiar absence of NH⋯OC hydrogen bonds in peptoids unveils the role of intramolecular backbone-to-backbone CO⋯CO interactions and CH⋯OC hydrogen bonds in the stabilization of the macrocycle conformation. Moreover, intramolecular backbone-side chain C5 CH⋯OC hydrogen bonds emerge as a stabilizing factor.We report novel, ribosomally incorporatable, and intramolecularly cysteine-reactive fluorobenzoic acid-derived linkers for SELEX of mRNA-displayed unnatural peptides, which spontaneously cyclized via intramolecular nucleophilic aromatic substitutions forming thioethers. With this strategy we identified several novel PCSK9-binding peptides.The environment around the active site affects the catalytic activity of enzymes. Studying the cucurbit[7]uril-promoted acid hydrolysis of a cationic phenyl acetate derivative, we found that the hydrophobic cavity of the macrocycle screens the reaction centre from the positively charged neighbouring group. Moreover, the chelation of alkali metal cations with the cucurbit[7]uril portal and acetyl group of the substrate reduces the hydrolysis rate of the encapsulated ester in an aqueous solution. This type of inhibition corresponds to a rare uncompetitive model in contrast to the more common competitive model that relies on substrate displacement.Terpenoids constitute a broad class of natural compounds with tremendous variability in structure and bioactivity, which resulted in a strong interest of the chemical community to this class of natural products over the last 150 years. The presence of strained small rings renders the terpenoid targets interesting for chemical synthesis, due to limited number of available methods and stability issues. In this feature article, a number of recent examples of total syntheses of terpenoids with complex carbon frameworks featuring small rings are discussed. Specific emphasis is given to the new developments in strategical and tactical approaches to construction of such systems.In order to make the drug specifically aggregate at the tumor site, we had developed a targeted drug delivery system based on pH responsive mesoporous silica nanoparticles. Mesoporous silica nanoparticles (MSN-COOH) were prepared and doxorubicin (DOX) was loaded into the pores of MSN-COOH, and then polyethyleneimine (PEI) and anisamide (AA) were modified on the surface of mesoporous silica, named DOX@MSN-PEI-AA(DMPA). DMPA specifically entered tumor cells through AA-mediated receptor endocytosis; PEI dissociated from the surface of the MSN in the acidic environment of cellular lysosomes/endosomes due to protonation of PEI, resulting in steady release of the encapsulated DOX from the pores of MSN in the cytoplasm of the target cells. In vitro and in vivo anti-tumor experiments and hemolytic experiments indicated that DMPA can accurately target breast cancer cells and show excellent safety at the same time, showing great potential for tumor therapy.A perylene five-membered ring diimide, PDI39, was developed as a new electron-deficient building block for n-type semiconductors. The π-expanded conjugated molecules containing azulenes were synthesized from PDI39. These conjugated molecules show helical geometry and near-infrared absorption up to 810 nm.Here, we report the highly active and selective electrocatalytic reduction of NO2- ions to value-added NH3 over a single-atom Ru-modified Cu nanowire array on three-dimensional copper foam (Ru-Cu NW/CF) under ambient conditions. The obtained Ru-Cu NW/CF catalyst exhibited a maximum faradaic efficiency of 94.1% and an NH3 yield up to 211.73 mg h-1 cm-2 (0.732 mmol h-1 cm-2), which was approximately five times higher than that of the Cu NW/CF catalyst.The kynurenine metabolite is associated with many diseases and disorders, ranging from diabetes and sepsis to more recently COVID-19. Here we report a fluorescence-based assay for the detection of kynurenine in urine using a specific chemosensor, 3-formyl-4-(ethylthio)-7-(diethylamino)-coumarin. The assay produces a linear response at clinically relevant ranges (1-20 μM), with a limit of detection of 0.7 μM. The average standard addition recoveries of kynurenine in synthetic urine samples are near to 100%, and the relative standard deviation values are less than 8%. The established fluorescence assay for quantitative analysis of kynurenine in urine is facile, sensitive and accurate and holds great potential for low-cost and high-throughput analysis of kynurenine in clinical laboratory settings.Halogen bonding of neutral donors using imine groups of porous organic cage compounds as acceptors leads to the formation of halogen-bonded frameworks. We report the use of two different imine cages, in combination with three electron-poor halogen bond donors. Four resulting solid-state structures elucidated by single-crystal X-ray analysis are presented and analysed for the first time by plane-wave DFT calculations and QTAIM-analyses of the entire unit cells, demonstrating the formation of halogen bonds within the networks. The supramolecular frameworks can be obtained either from solution or mechanochemically by liquid-assisted grinding.Hydrazone-linked covalent organic framework-43 (COF-43) was synthesized and the carbon paste electrode (CPE) modified with this COF was used as a voltammetric sensor to measure silver(I). Various characterization tests (XRD, FTIR, BET, SEM/EDX, electrochemical impedance (EIS), and cyclic voltammetry (CV)) were performed on the synthesized COF-43 and the prepared COF-43/CPE. Box-Behnken design was used to optimize the preparation and operation conditions of the sensor. EIS and CV investigations reveal the diffusive characteristics of silver transport in the electrode matrix. An appropriate mechanism for the sensor procedure has been suggested and ratified by electrochemical and SEM/EDX techniques. https://www.selleckchem.com/products/cyclo-rgdyk.html The COF-43 used has several recognition elements for the selective binding of silver ion and due to its high porosity provides a large space for the deposition and reduction of large amounts of silver. Therefore, due to the correct selection of COF used in the construction of the sensor, high selectivity and sensitivnsor.Technologies for preservation of specimens in the absence of cold chains are essential for optimum utilization of existing laboratory services in the developing world. We present a prototype called specimen transportation tube (SPECTRA-tube) for the collection, exposure-free drying, ambient transportation, and liquid state recovery of large-volume (>1 mL) specimens. Specimens introduced into the SPECTRA-tube are dried in glass fiber membranes, which are critical for efficient liquid-state sample recovery by rehydration and centrifugation. SPECTRA-tube is demonstrated for the dry storage of sputum for tuberculosis detection. Mycobacterium smegmatis (Msm)-spiked mock sputum dried in a native Standard 17 glass fiber was stable for molecular testing after 10 day storage at 45 °C and for culture testing after 10- and 5-day storage at 37 °C and 45 °C, respectively. Compatibility with human sputum storage was demonstrated by dry storing 1.2 mL Mycobacterium bovis-spiked human sputum in a SPECTRA-tube for 5 days at room temperature. We have thus demonstrated the first workflow for dry storage of sputum followed by molecular and culture testing. Compared to existing specimen dry storage technologies, SPECTRA-tube significantly increases the volume of liquid specimens that can be transported in the dry state and enables the recovery of the entire sample in the liquid state, rendering it compatible with conventional downstream analysis methods.A one-step side-by-side 3D printing method is proposed to construct linear lithium-, sodium-, and zinc-ion full batteries with high electrochemical performance. The inks of the battery components present shear thinning characteristics and can be printed on different substrates. This approach to design high performance linear full batteries is a general strategy.Crystallization of supercooled liquid water in most natural environments starts with heterogeneous nucleation of ice induced by a nucleation site. Mineral surfaces, which form the majority of aqueous interfaces in Earth's ecosystem, possess a plethora of surface morphological and chemical features that can serve as ice nucleation sites. The nature of surface sites responsible for ice nucleation from supersaturated water vapor have been recently identified for alkali feldspar, a family of rock-building minerals constituting 60% of the Earth's crust. It was demonstrated that ice preferentially forms upon the patches of crystalline surface with (100) orientation, exposed in the surface defects such as cracks, pores, and pits arising due to chemically induced stress and further enhanced by hydrothermal alterations of natural feldspars. However, whether the same sites were responsible for nucleation from liquid water, remained to be shown. Here, we investigate the mechanism of heterogeneous ice nucleation in a layer of aqueous sucrose solution on top of thin sections of feldspar prepared along the (010) crystalline plane.
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