Hermansenbutcher9292
© FEMS 2020.Continuous efforts have been invested in the selective modification of proteins. Herein, we first report the construction of sulfonium tethered cyclic peptides via an intramolecular cyclization by an aliphatic halide. This cyclization could enhance the stability and cellular uptake of peptides. Furthermore, the sulfonium center could be recognized by cysteine in the vicinity of the protein-peptide interacting interface and form a peptide-protein conjugate.Second near-infrared window (NIR-II, 1000-1700 nm) absorption and fluorescent agents have attracted great attention because they can overcome the penetration limitation of the first near-infrared window (NIR-I, 750-1000 nm). However, these always "on" agents face the severe problem of being susceptible to retention and phagocytosis by the reticuloendothelial system after intravenous administration, which results in signal interference during diagnosis and side effects during treatment. Accordingly, tumor microenvironment-responsive smart agents (smart NIR-II agents), whose imaging and therapeutic functions can only be triggered in tumors, can overcome this limitation. Thus, NIR-II smart agents, which exhibit a combined response to the tumor microenvironment and NIR-II, make full use of the advantages of both triggers and improve the precision diagnosis and effective treatment of cancer. This review summarizes the recent advances in tumor microenvironment-activated NIR-II agents for tumor diagnosis and treatment, including smart NIR-II fluorescence imaging, photoacoustic imaging, photothermal therapy and photodynamic therapy. Finally, the challenges and perspectives of NIR-II smart agents for tumor diagnosis and treatment are proposed.Known hydrophilic halide salts of the title compounds are converted to new lipophilic BArf- (B(3,5-C6H3(CF3)2)4-) salts. These are isolated as hydrates (Λ- or Δ-[M(en)3]n+ nBArf-·zH2O; z = 17-9) and characterized by NMR (acetone-d6) and microanalyses. Thermal stabilities are probed by capillary thermolyses and TGA and DSC measurements (onset of dehydration 71-151 °C). In the presence of tertiary amines, they are effective catalysts for enantioselective Michael type carbon-carbon or carbon-nitrogen bond forming additions of 1,3-dicarbonyl compounds (acceptors trans-β-nitrostyrene, di-tert-butylazodicarboxylate, 2-cyclopenten-1-one; average ee = 33%, 52%, 17%). Effects of the metal and charge upon enantioselectivities are analyzed. A number of properties appear to correlate to the NH Brønsted acidity order ([Pt(en)3]4+ > [Cr(en)3]3+ > [Co(en)3]3+ > [Rh(en)3]3+ > [Ir(en)3]3+).It remains elusive as to how exactly the site-specific atom in a catalyst can induce a chemical reaction mainly due to the observed catalytic performance from an ensemble average of all active atoms in the catalyst. In this work, we have reported the catalytic properties of four metal clusters (namely, Au8Pd, Au9, Au24Pd and Au25) for the oxidation of benzyl alcohol. It was found that the Pd atom in the Au8Pd cluster is likely to be a key to catalyze the oxidation reaction, in which the Pd atom can provide an active site to adsorb and activate O2. Our calculation study suggests that the high catalytic activity of the Au8Pd cluster is due to the unique ability of Au8Pd to mediate the electrons and holes of the adsorbates. This work provides a feasible strategy to enable highly efficient chemical processes via precisely doping foreign atoms into catalysts with atomic precision.A chemically-triggered signalling cascade between cucurbituril host-guest complexes by means of multi-step competitive displacement is demonstrated. The inter-complex communication of chemical information yields the release of bio-relevant cargo, reminiscent of cellular signalling pathways.Flow-assembled chitosan membranes are robust and semipermeable hydrogel structures formed in microfluidic devices that have been used for important applications such as gradient generation and studying cell-cell signaling. One challenge, however, remains unresolved. When a polydimethylsiloxane (PDMS) microchannel with a flow-assembled, deprotonated chitosan membrane (DCM) is treated with anti-adhesion agents such as Pluronic F-127 to prevent biomolecular and cellular adsorption on PDMS, the interaction between DCM and PDMS is compromised and the DCM easily delaminates. To address this challenge, DCMs in microfluidics are crosslinked with glutaraldehyde to modulate their properties, and the altered properties of the glutaraldehyde treated chitosan membrane (GTCM) are investigated. First, the GTCM's acidic resistance was confirmed, its mechanical robustness against hydrostatic pressure was significantly improved, and it remained intact on PDMS after Pluronic treatment. Second, crystallization in DCM and GTCM was investigated with quantitative polarized light microscopy (qPLM), which revealed that GTCM's optical retardance and anisotropy were lower, implying less molecular alignment than in DCM. Finally, membrane permeability was tested with FITC-labeled dextran transport experiments, which showed that the transport across GTCM was slightly higher than that across DCM. Overall, glutaraldehyde-crosslinked chitosan membrane has better acidic resistance, higher strength under Pluronic treatment, and less molecular microalignment, while its semi-permeability is retained. This study demonstrates how glutaraldehyde crosslinking can be used to modify and improve biopolymer membrane properties for broader applications, such as in an acidic environment or when Pluronic passivation is needed.Herein, we report a turn-on fluorimetric nanoprobe for intracellular glutathione (GSH) imaging. https://www.selleckchem.com/products/tauroursodeoxycholic-acid.html The principle of this probe is designed on the basis of the selective reduction between GSH and disulfide bond-based self-crosslinked red emissive carbon dots (abbreviated as SCCDs). The nanoprobe (i.e., SCCDs) was facilely fabricated from thiol-modified carbon dots (CDs) through oxidation in the presence of H2O2, and its fluorescence was greatly reduced due to the effect of aggregation induced quenching (AIQ). However, in the presence of GSH, the SCCDs were separated into many single CDs. As a result, the fluorescence of the nanoprobe was recovered in a GSH concentration-dependent manner, which is the basis for the quantitative analysis of GSH. The nanoprobe shows excellent specificity and a linear range from 0 to 0.15 mM towards GSH with a limit of detection (LOD) of 5.7 μM. Finally, the nanoprobe was demonstrated to have extremely low cytotoxicity, and was successfully applied for monitoring the GSH level in living cells.