Notes

OnePot PURE Cell-Free System.
The fabrication of polymethyl methacrylate (PMMA) latexes armored with modified Fe3O4 (IO) nanoparticles by Pickering emulsion polymerization was described. Dynamic light scattering analyzed the IO/PMMA latex particle size. Thermogravimetric analysis evaluated the incorporation efficiency (IE) of IO nanoparticles and the surface coverage (Cov) of latex particles. Scanning electron microscopy confirmed the IO nanoparticles loaded on the latex surface. Both the original and dialyzed IO nanoparticles were used as stabilizers to discuss the influence of electrolytes in IO solution on the process of emulsion polymerization. In order to effectively control the IE, Cov, hydrophobic properties, and magnetization of latex particles, the kinds of monomers, pH, and solid content of dialyzed IO on the polymerization process were investigated. In addition, the conversion of monomers, the size, and the number of latex particles were learned deeply so as to reveal the key mechanism of the PMMA polymerization process in the absence of electrolytes. Moreover, IO/PMMA latex particles showed good magnetic properties and emulsifying ability. In view of these results, a simple and efficient method for preparing magnetic hybrid materials by Pickering emulsion polymerization was proposed.Here, we employ the CASPT2//CASSCF and QM(CASPT2//CASSCF)/MM approaches to explore the photochemical mechanism of homomenthyl salicylate (HMS) in vacuum and an acetonitrile solution. The results show that in both cases, the excited-state relaxation mainly involves a spectroscopically "bright" S1(1ππ*) state and the lower-lying T1 and T2 states. In the major relaxation pathway, the photoexcited S1 keto system first undergoes an essentially barrierless excited-state intramolecular proton transfer (ESIPT) to generate the S1 enol minimum, near which a favorable S1/S0 conical intersection decays the system to the S0 state followed by a reverse ground-state intramolecular proton transfer (GSIPT) to repopulate the initial S0 keto species. In the minor one, an S1/T2/T1 three-state intersection in the keto region makes the T1 state populated via direct and T2-mediated intersystem crossing (ISC) processes. In the T1 state, an ESIPT occurs, which is followed by ISC near a T1/S0 crossing point in the enol region to the S0 state and finally back to the S0 keto species. In addition, a T1/S0 crossing point near the T1 keto minimum can also help the system decay to the S0 keto species. However, small spin-orbit couplings between T1 and S0 at these T1/S0 crossing points make ISC to the S0 state very slow and make the system trapped in the T1 state for a while. The present work rationalizes not only the ultrafast excited-state decay dynamics of HMS but also its low quantum yield of phosphorescence at 77 K.Although a myriad of bioorthogonal prodrugs have been developed, very few of them present both fast reaction kinetics and complete cleavage. Herein, we report a new bioorthogonal prodrug strategy with both fast reaction kinetics (k2 ∼103 M-1 s-1) and complete cleavage (>90% within minutes) using the bioorthogonal reaction pair of N-oxide and boron reagent. Distinctively, an innovative 1,6-elimination-based self-immolative linker is masked by N-oxide, which can be bioorthogonally demasked by a boron reagent for the release of both amino and hydroxy-containing payload in live cells. Such a strategy was applied to prepare a bioorthogonal prodrug for a camptothecin derivative, SN-38, resulting in 10-fold weakened cytotoxicity against A549 cells, 300-fold enhanced water solubility, and "on-demand" activation upon a click reaction both in vitro and in vivo. This novel bioorthogonal prodrug strategy presents significant advances over the existing ones and may find wide applications in drug delivery in the future.Functionalization of silk fibroin hydrogel with antimicrobial activity is essential for promoting the applications of this excellent biomaterial. In this work, a simple approach based on electrostatic interaction is adopted to produce antimicrobial silk hydrogel containing an antimicrobial peptide (AMP), polymyxin B, an important last-line antibiotic to treat multidrug-resistant bacterial superbugs. The polycationic property of this peptide and the negative charge of silk fibroin lead to strong interactions between them, as demonstrated by changes in nanofibril structure, gelation kinetics, ζ-potential, fluorescence emission, and rheological properties of the gel. The hydrogels loaded with polymyxin B demonstrated antimicrobial activity against two Gram-negative bacterial strains. A combination of the results from the different characterizations suggests that the optimal molar ratio of polymyxin B to silk fibroin is 12.5. As most AMPs are cationic, this electrostatic approach is suitable for the straightforward functionalization of inert silk hydrogel with other AMPs.The transformational effect of photoredox catalytic chemistries has inspired new opportunities, enabling us to interrogate nature in ways that are not possible otherwise and to unveil new biotechnologies in therapy and diagnosis. However, the deployment of artificial photoredox catalysis in living systems remains challenging, mired by the off-target risk and safety concerns of photocatalyst toxicity. Here, we present an appealing approach, namely conditionally activatable photoredox catalysis (ConAPC), and as a proof of concept design the first ConAPC architecture (Se-NO2) based upon classic self-immolative chemistry, in which the inherent photocatalytic properties can be temporarily caged while the species becomes active only at the tumor sites via sensing to specific biomarkers. Such a masking strategy allows a spatial-temporal control of photoresponsivity in vitro and in vivo. In particular, for ConAPC design, a new biologically benign metal-free photocatalyst (Se-NH2), which is able to initiate NIR photoredox catalysis to manipulate the cellular electron pool in an O2-independent mechanism of action, is identified. HDAC inhibitor With this unique strategy, potent tumor-specific targeting photocatalytic eradication (TGI 95%) is obtained in a mouse model. Impressively, favorable features such as high-resolution tumor recognition (SBR 33.6) and excellent biocompatibility and safety are also achieved. This work therefore offers a new possibility for chemists to leverage artificial photocatalytic reactions toward the development of facile and intelligent photocatalytic theranostics.Droplet-based microfluidic systems are a powerful tool for biological assays with high throughput. Water-in-oil droplets (WODLs) are typically used in droplet-based microfluidic systems to culture microorganisms and perform enzyme assays. However, because of the oil surrounding the nanoliter and picoliter volumes of WODLs, availability of suitable substrates is limited. For instance, although 7-amino-4-methylcoumarin (AMC) is commonly used as a fluorescent probe of the substrate to detect peptidase activity, AMC leaks from WODLs to the oil phase due to its high hydrophobicity. Thus, AMC substrates cannot be used in droplet-based microfluidic systems with WODLs. In this study, we developed a peptidase substrate consisting of a dipeptide and 7-aminocoumarin-4-acetic acid (ACA), an AMC-derived fluorogenic compound. ACA was retained in the WODL for more than 7 days, and the dipeptidyl ACA substrate detected dipeptidyl peptidase (DPP) activity in the WODL. Compared to AMC substrates, the substrate specificity constants of DPPs for ACA substrates increased up to 4.7-fold. Fluorescence-activated droplet sorting made high-throughput screening of microorganisms based on DPP activity using the dipeptidyl ACA substrate possible. Since ACA could be applied to various substrates as a fluorescent probe, detectable microbial enzyme activities for droplet-based microfluidic systems can be largely expanded.Two-dimensional (2D) covalent-organic frameworks (COFs) offer abundant hollow sites for stably anchoring transition-metal (TM) atoms to promote single-atom catalysis (SACs), which is expected to overcome the poor stability of SACs on conventional substrate materials. Using first-principles calculations within density-functional theory, a number of TM atoms embedded on a 2D COF Pc-TFPN (TMPc-TFPN) as SACs for ammonia synthesis under ambient conditions are investigated. Through a "five-step" screening strategy, WPc-TFPN is highlighted from 26 TMPc-TFPNs as the best SACs for nitrogen reduction reaction (NRR) with a low limiting potential of -0.19 V. Meanwhile, multiple-level descriptors are developed to uncover the origins of NRR activity, among which a simple descriptor φ that involves the electronegativity and number of d electrons of TM atoms shows volcano plot trends of limiting potential of NRR. This work provides a rational strategy for fast screening SACs for the electrochemical N2 fixation using 2D COFs containing TM-N4 units as host materials, which could also be applied to other electrochemical reactions.A powerful tris(4-bromophenyl)aminium hexachloroantimonate (BAHA) mediated regioselective intermolecular coupling reaction of vindoline with a wide range of substrates that include β-ketoesters, β-diketones, β-ketoaldehydes, β-ketonitriles, β-ketolactones, β-ketolactams, β-cyanoesters, and malononitriles is detailed. The BAHA-promoted intermolecular sp3/sp2 coupling, representing a special class of selective C-H functionalization reactions with direct carbon-carbon bond formation, proceeds with generation of a quaternary center bound to the aryl C15 center of vindoline capable of accommodating of the vinblastine C16' methyl ester and functionalized for subsequent divergent heterocycle introduction. A comprehensive examination of the reaction scope, optimization of subtle reaction parameters, and key insights into the reaction mechanism are described. Contrary to what might be prevailing expectations, studies suggest the plausible mechanism entails initial single-electron oxidation of the substrate enolate, not vindoline, and subsequent regiospecific addition of the resulting electrophilic radical to vindoline. As such and beyond the new arylation reaction with vindoline, the studies define a host of new, previously unrecognized, applications of BAHA and related triarylaminium radical cations that arises from their ability to generate stabilized electrophilic radicals from β-ketoesters and related substrates under nonreducing and metal-free conditions. Those exemplified herein include mediating stabilized enolate free radical arylation, dimerization, allylation, alkene addition, and α-oxidation reactions.Detection of pathogenic bacteria is of vital significance for combating and preventing infectious diseases. In this work, we developed a multivalent aptamer probe (Multi-VAP)-based trigging isothermal circular amplification (TICA) for rapidly and ultrasensitively detecting Salmonella. In this sensing system, the fluorescence of Multi-VAP was strongly quenched via the dual effect of FRET. Introduction of Salmonella to the system forced the configuration change of Multi-VAP, leading to the occurrence of a TICA responsible for tuning all of the fluorescence-quenched Multi-VAP into a complete restoration state. This prominent feature allows the reasonable combination of a strong background restraint and great target signal amplification into one sensing system, which in turn benefits the improvement of the signal-to-noise ratio to ensure that the system has an ultrahigh sensitivity. Combined with the employment of an aptamer to ensure that it has excellent specificity, the Salmonella can be quantitatively and qualitatively analyzed even from human serum.
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