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51.
An applicable and easy-handling Ni-catalyst can be used to promote direct arylation of α-bromonitriles with various arylboronic acids to construct α-arylnitriles under mild conditions. The methodology tolerates β-hydrogens and functional groups in the substrates.  相似文献   
52.
Lithium-selenium (Li-Se) battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed pol...  相似文献   
53.
54.
    
Bioconjugation, a synthetic tool that endows small molecules with biocompatibility and target specificity through covalent attachment of a biomolecule, holds promise for next-generation diagnosis or therapy. Besides the establishment of chemical bonding, such chemical modification concurrently allows alteration of the physicochemical properties of small molecules, but this has been paid less attention in designing novel bioconjugates. Here, we report a “two birds one stone” methodology for irreversible porphyrin bioconjugation based on β-fluoropyrrolyl-cysteine SNAr chemistry, in which the β-fluorine of porphyrin is selectively replaced by a cysteine in either peptides or proteins to generate novel β-peptidyl/proteic porphyrins. Notably, due to the distinct electronic nature between fluorine and sulfur, such replacement makes the Q band red-shift to the near-infrared region (NIR, >700 nm). This facilitates intersystem crossing (ISC) to enhance the triplet population and thus singlet oxygen production. This new methodology features water tolerance, a fast reaction time (15 min), good chemo-selectivity, and broad substrate scope, including various peptides and proteins under mild conditions. To demonstrate its potential, we applied porphyrin β-bioconjugates in several scenarios, including (1) cytosolic delivery of functional proteins, (2) metabolic glycan labeling, (3) caspase-3 detection, and (4) tumor-targeting phototheranostics.

This work demonstrates ‘two birds one stone’ β-fluoropyrrolyl-cysteine SNAr chemistry. This methodology not only achieves porphyrin peptide/protein conjugates but also induces attractive porphyrinic photophysical properties to facilitate promising biological applications.  相似文献   
55.
    
In this study, an aluminum (Al) foil used for lithium ion battery packaging film was treated with titanium (Ti)/zirconium (Zr) solution containing hexafluorotitanic acid and hexafluorozirconic acid using tannic acid as a colorant and metavanadate as an accelerator, respectively, and a golden conversion coating was successfully deposited on the surface of Al foil. The morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy, and the hydrophilicity was assessed by contact angle measurement. The effect of Ti/Zr treatment on the adhesion properties of Al foil was evaluated by T-peeling test and compared with that of traditional chromate-phosphate treatment. The results show that tannic acid contributes to the formation of the golden coating, and metavanadate accelerates the formation of the conversion coating. The results also indicate that the Ti/Zr-based conversion coating is mainly composed of Al2O3, Al (OH)3, AlF3, TiO2/ZrO2, NH4VO3, and V2O5. The Ti/Zr treatment cannot only improve the heat-sealing strength, but also the T-peeling strength by approximately 12 times compared with that of untreated Al foil. Thus, Ti/Zr treatment has the potential to replace the traditional chromate conversion treatment.  相似文献   
56.
    
Herein, we present the efficient isomerization of epoxides into methyl ketones with a novel pincer-rhodium complex under very mild conditions. The catalyst system has an excellent functional group tolerance and a wide array of epoxides was tested. The corresponding methyl ketones were obtained in very high yields with excellent chemo- and regioselectivity. In addition, we investigated mechanistic details like the isomerization of the catalyst, and we obtained evidence that the catalytic cycle follows a β-hydride elimination-reductive elimination pathway after the nucleophilic ring opening of the epoxide.  相似文献   
57.
    
Metal-organic frameworks (MOFs)-derived materials are widely applied in functional materials with noble structures. Here, a well-designed strategy for generating hierarchical double-shelled nanoboxes is reported. Starting from the construction of hierarchical MOF-on-MOF architecture followed by a post-annealing treatment, hierarchical TiO2@Co3O4 nanoboxes are successfully synthesized with an interior TiO2 shell supporting the outer hollow-Co3O4-aggregates shell with a CoTiO3 intermediate layer. The TiO2@Co3O4 electrode displays a superior lithium storage performance in terms of high reversible capacity (920.5 mAh g−1 after 150 cycles at 200 mA g−1, 58.6 % higher than theoretical capacity), outstanding high-rate long-term cycling stability (838.6 mAh g−1 after 600 cycles at 1000 mA g−1, 44.5 % higher than theoretical capacity), and remarkable rate capability (good restorability at 2000 mA g−1). Furthermore, the morphology and electrochemical kinetic analysis proves that TiO2@Co3O4 has a more stable structure, higher capacitive contribution, and better Li-ion diffusion, which enhance the lithium-storage performance.  相似文献   
58.
    
Colon cancer (CC) is one of the most common intestinal malignancies and is difficult to detect in its early stage by magnetic resonance imaging (MRI) with currently used contrast agents (CAs). The development of targeted CAs contributes to the early diagnosis of CC and thereby enables early intervention and timely therapy. Considering the outstanding performance of upconversion nanoprobes (UCNPs) in high‐performance MR and fluorescence imaging, a new type of nanoprobes with considerably enhanced imaging performance is developed herein. Carcinoembryonic antigen (CEA) antibody is conjugated onto the surface of UCNPs to achieve the targeted imaging of early CC tumors, which overexpress CEA. Both toxicity tests and histological/hematological examinations demonstrate the excellent biocompatibility of these CC‐targeting nanoprobes, which possess great potential for clinical application in the early diagnosis of CC.  相似文献   
59.
    
The Gerchberg–Saxton (G-S) algorithm is a phase retrieval algorithm that is widely used in beam shaping and optical information processing. However, the G-S algorithm has difficulty obtaining the exact solution after iterating, and an approximate solution is often obtained. In this paper, we propose a series of modified G-S algorithms based on the Fresnel transform domain, including the single-phase retrieval (SPR) algorithm, the double-phase retrieval (DPR) algorithm, and the multiple-phase retrieval (MPR) algorithm. The analysis results show that the convergence of the SPR algorithm is better than that of the G-S algorithm, but the exact solution is not obtained. The DPR and MPR algorithms have good convergence and can obtain exact solutions; that is, the information is recovered losslessly. We discuss the security advantages and verification reliability of the proposed algorithms in image encryption. A multiple-image encryption scheme is proposed, in which n plaintexts can be recovered from n ciphertexts, which greatly improves the efficiency of the system. Finally, the proposed algorithms are compared with the current phase retrieval algorithms, and future applications are discussed. We hope that our research can provide new ideas for the application of the G-S algorithm.  相似文献   
60.
    
We investigate the structure of a large precision matrix in Gaussian graphical models by decomposing it into a low rank component and a remainder part with sparse precision matrix.Based on the decomposition,we propose to estimate the large precision matrix by inverting a principal orthogonal decomposition(IPOD).The IPOD approach has appealing practical interpretations in conditional graphical models given the low rank component,and it connects to Gaussian graphical models with latent variables.Specifically,we show that the low rank component in the decomposition of the large precision matrix can be viewed as the contribution from the latent variables in a Gaussian graphical model.Compared with existing approaches for latent variable graphical models,the IPOD is conveniently feasible in practice where only inverting a low-dimensional matrix is required.To identify the number of latent variables,which is an objective of its own interest,we investigate and justify an approach by examining the ratios of adjacent eigenvalues of the sample covariance matrix?Theoretical properties,numerical examples,and a real data application demonstrate the merits of the IPOD approach in its convenience,performance,and interpretability.  相似文献   
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