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51.
A single-step method for isolation of specific cells based on multiple surface markers will have unique advantages because of its scalability, efficacy, and mildness. Herein, we developed multi-aptamer-mediated proximity ligation method on live cell membranes that leverages a multi-receptor co-recognition design for enhanced specificity, as well as a robust in situ signal amplification design for improved sensitivity of cell isolation. We demonstrated the promising efficacy of our method on differentiating tumor cell subtypes in both cell mixtures and clinical samples. Owing to its simple and fast operation with excellent cell isolation sensitivity and accuracy, this approach will have broad applications in biological science, biomedical engineering, and personalized medicine.  相似文献   
52.
Three novel amphiphilic poly(ionic liquid) (PIL)/Wells–Dawson-type phosphovanadomolybdate (V-POM) ionic composites with tunable oxidative catalytic activity and unique nanostructure were synthesized using carboxylic acid-functionalized PIL and H7[P2Mo17VO62], H8[P2Mo16V2O62] and H9[P2Mo15V3O62] as synthetic units via self-assembly in water. The results of characterization indicated that V-POM anions were finely dispersed in the PIL cation framework, and their structures were well preserved. The three composites are amorphous V-POM salts of PIL cation with a considerable thermal stability, and an open three-dimensional network structure with hierarchical porosity. The as-synthesized composites were found to be efficient heterogeneous catalysts for the direct hydroxylation of benzene to phenol with H2O2 in the liquid phase. Under optimum conditions, a phenol yield of 37.3% was achieved with selectivity of 100%. The high catalytic performance could be attributed to the synergistic catalytic effect between V-POM anion and carboxylic acid-functionalized PIL cation framework, and good benzene adsorption and phenol desorption ability of amphiphilic micropores in the structure of the composites. Additionally, these composites exhibited high stability under the reaction conditions and could be easily recovered and reused at least six times without noticeably loss of activity.  相似文献   
53.
Herein a well-sealed and thermostated kinetics assembly is designed and built, which can run stirred at different reaction temperatures. With the reaction assembly above and the volumetric method together, the hydrogen peroxide (H2O2) decomposition reaction kinetics is systematically investigated under a variety of reaction conditions over a copper-doped buserite-type layer manganese oxide (referred to as Cu-buserite) as a heterogeneous catalyst. The overall second-order rate law is fitted out by the linear regression analysis, with the reaction orders with respect to both H2O2 and Cu-buserite determined to each be equal to 1, and then explicitly explained by the proposed Michaelis-Menten like mechanism. The apparent activation energy Ea is estimated as 33.5 ± 2.5 kJ mol−1.  相似文献   
54.
The construction of nanoscopic materials by synthetic methodologies that iterate covalent and supramolecular interactions has been developed over the past three decades as a powerful method to afford complex functional materials. Indeed, the present study was nearly lost in the archives of dissertation research completed in 2001, which revealed nanoscale conformational dynamics in the segmental reorganization, and partial inversion, of topologically shell crosslinked knedel-like (SCK) nanoparticles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 204–214  相似文献   
55.
Recently, nonmetal doping has exhibited its great potential for boosting the hydrogen evolution reaction (HER) of transition-metal (TM)-based electrocatalysts. To this end, this work overviews the recent achievements made on the design and development of the nonmetal-doped TM-based electrocatalysts and their performance for the HER. It is also shown that by rationally doping nonmetal elements, the electronic structures of TM-based electrocatalysts can be effectively tuned and in turn the Gibbs free energy of the TM for adsorption of H* intermediates (ΔGH*) optimized, consequently enhancing the intrinsic activity of TM-based electrocatalysts. Notably, we highlight that concurrently doping two nonmetal elements can continuously and precisely regulate the electronic structures of the TM, thereby maximizing the activity for HER. Moreover, nonmetal doping also accounts for enhancing the physical properties of the TM (i.e. surface area). Therefore, nonmetal doping is a robust strategy for simultaneous regulation of the chemical and physical features of the TM.  相似文献   
56.
Lithium ion batteries (LIBs) at present still suffer from low rate capability and poor cycle life during fast ion insertion/extraction processes. Searching for high-capacity and stable anode materials is still an ongoing challenge. Herein, a facile strategy for the synthesis of ultrathin GeS2 nanosheets with the thickness of 1.1 nm is reported. When used as anodes for LIBs, the two-dimensional (2D) structure can effectively increase the electrode/electrolyte interface area, facilitate the ion transport, and buffer the volume expansion. Benefiting from these merits, the as-synthesized GeS2 nanosheets deliver high specific capacity (1335 mAh g−1 at 0.15 A g−1), extraordinary rate performance (337 mAh g−1 at 15 A g−1) and stable cycling performance (974 mAh g−1 after 200 cycles at 0.5 A g−1). Importantly, our fabricated Li-ion full cells manifest an impressive specific capacity of 577 mAh g−1 after 50 cycles at 0.1 A g−1 and a high energy density of 361 Wh kg−1 at a power density of 346 W kg−1. Furthermore, the electrochemical reaction mechanism is investigated by the means of ex-situ high-resolution transmission electron microscopy. These results suggest that GeS2 can use to be an alternative anode material and encourage more efforts to develop other high-performance LIBs anodes.  相似文献   
57.
Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE, single electron transfer (SET) in donor–acceptor complex (DAC) from *HE to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE. to sulfone by the DAC method.  相似文献   
58.
Layered/two-dimensional covalent organic frameworks (2D COF) are crystalline porous materials composed of light elements linked by strong covalent bonds. Interlayer force is one of the main factors directing the formation of a stacked layer structure, which plays a vital role in the stability, crystallinity, and porosity of layered COFs. The as-developed new way to modulate the interlayer force of imine-linked 2D TAPB-PDA-COF (TAPB = 1,3,5-tris(4-aminophenyl)benzene, PDA = terephthaldehyde) by only adjusting the pH of the solution. At alkaline and neutral pH, the pore size of the COF decreases from 34 Å due to the turbostratic effect. Under highly acidic conditions (pH 1), TAPB-PDA-COF shows a faster and stronger turbostratic effect, thus causing the 2D structure to exfoliate. This yields bulk quantities of an exfoliated few/single-layer 2D COF, which was well dispersed and displayed a clear Tyndall effect (TE). Furthermore, nanopipette-based electrochemical testing also confirms the slipping of layers with increase towards acidic pH. A model of pH-dependent layer slipping of TAPB-PDA-COF was proposed. This controllable pH-dependent change in the layer structure may open a new door for potential applications in controlled gas adsorption/desorption and drug loading/releasing.  相似文献   
59.
The enantioselective synthesis of α-thiocarboxylic acids by biocatalytic dynamic kinetic resolution (DKR) of nitrile precursors exploiting nitrilase enzymes is described. A panel of 35 nitrilase biocatalysts were screened and enzymes Nit27 and Nit34 were found to catalyse the DKR of racemic α-thionitriles under mild conditions, affording the corresponding carboxylic acids with high conversions and good-to-excellent ee. The ammonia produced in situ during the biocatalytic transformation favours the racemization of the nitrile enantiomers and, in turn, the DKR without the need of any external additive base.  相似文献   
60.
Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT-(ZnP)2 and TAT-(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.  相似文献   
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