Latest ArticlesA sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
Acenapththylene-imide (AnI), similar to naphthalene diimide (NDI), is an outstanding building block for organic functional materials and has gained a lot of research attention. Herein, Sulphur and Selenium-embedded AnI-containing polycyclic aromatic hydrocarbon molecules, AnI-SQ and AnI-SeQ, with [1, 2, 5]thiadiazolo [3, 4-g]quinoxaline (SQ) and [1, 2, 5]selenadiazolo [3, 4-g]quinoxaline (SeQ) are designed and synthesized with low-lying LUMO energy levels. The absorption and emission of AnI-SQ and AnI-SeQ displayed a bathochromic shift upon protonation of the C = N bond. Besides, theoretical calculation indicates remarkable rigid planar backbones for both AnI-SQ and AnI-SeQ. Through self-assembly with polymeric Pluronic® F-127, corresponding hydrophilic nanoparticles (NPs) were prepared with low cytotoxicity. And AnI-SQ NPs could be applied for in vitro two-photon fluorescence imaging.
Over the last decade, numerous research efforts have been devoted to pillar [n]arenes since their debut. The popularity of pillararenes is a reflection of current research trend in supramolecular and macrocyclic chemistry in general. Among the vast applications (such as chemosensors, drug delivery, transmembrance channels, and separation) of pillararenes, their utilization in catalysis is a relatively less explored area. However, soaring attention has been paid by researchers in recent years and this field has seen gradual increasing publications. Therefore, in this review we will discuss progress in the emerging applications of pillararene architectures in catalysis based on various reaction genre including reduction, oxidation, coupling, decomposition and others. Furthermore, this review not only focuses on the pillararenes based current progress in catalysis, but also provides the signs for future development in this research field.
Microarray technology has been widely applied in biomedical research. The key to microarray study is to develop efficient immobilization method. In this study, we designed a new reversible microarray immobilization method based on thiol-quinone reaction. A quinone-functionalized slide was fabricated through H2O2 treatment of dopamine-coated slides. Various thiol-containing molecules can be anchored onto the quinone-functionalized slides via thioether linker, which could be cleaved under H2O2 treatment to regenerate quinone groups on the surface. The highly versatile approach can be widely used for immobilization of various thiol-containing molecules.
Selenization reaction with the in situ prepared NaHSe has been successfully developed to occur in aqueous solution. The technique affords a method to upload the bioactive Se element on cotton products in semi-industrial scale. The antibacterial tests revealed that the selenized cotton possessed a potent and prolonged antimicrobial effect against both Gram-positive S. aureus and Gram-negative E. coli bacteria. This work discloses a practical method for preparing the selenium-containing antibacterial materials concisely and directly with industrial application potential.
Photothermal therapy (PTT)-induced immune response has attracted much attention, however, which cannot work at full capacity. In this study, the simvastatin (SV) adjuvant is loaded into gold nanocages (AuNCs) to develop a simple drug delivery system, which can efficiently utilize the tumor-associated antigens (TAAs) for improving immune responses. AuNCs/SV-mediated PTT treatment enhances tumor cells damage and promotes the release of TAAs which are immediately captured by AuNCs/SV to form AuNCs/SV/TAAs recombinant nanoparticle. Impressively, AuNCs/SV/TAAs can accumulate in lymph nodes effectively due to the suitable size of ~55 nm and hyperthermia-induced vasodilative effect. And the co-delivery of antigen and adjuvant is beneficial to stimulating the maturation of dendritic cells for further activating T cells. In a word, the recombinant strategy could make full use of TAAs to produce an individual powerful immunotherapy.
Based on the host-guest molecular recognition capability of cucurbit[6]uril (CB[6]) modified on the gold surface, sensitive spectrophotometric and electrochemical methods for the detection of metformin (MET) have been developed. The molecular recognition between cucurbit[7]uril (CB[7]) or CB[6] and MET is initially demonstrated and the related recognition mechanism is further deliberated. First, CB[6]-modified gold nanoparticles (AuNPs/CB[6]) were synthesized and then characterized by ultraviolet visible light spectrum (UV–vis) and transmission electron microscopy (TEM). The aggregation of AuNPs/CB[6] prompted by MET triggered changes of color and the absorption spectrum, that explored for the visual identification and spectrophotometric determination of MET. Under the optimized detection conditions, the UV–vis spectrometry had a good linear relationship in the range of 6–700 µmol/L, and the detection limit was 2 µmol/L. In addition, a single-layer CB[6]-modified gold electrode (GE-CB[6]) detection system for MET was constructed. As the concentration of MET in the solution continues to increase, the charge transfer resistance (Rct) in the Nyquist diagram of the electrochemical impedance method (EIS) continues to increase. In the concentration range from 10 pmol/L to 20 nmol/L, the logarithm of the MET concentration has a good linear relationship with Rct, and the detection limit of this method is 1.35 pmol/L. Both methods have good concentration sensitivity to MET in different concentration ranges, providing a powerful tool for the detection of MET.
White-light-emitting diodes (WLEDs) possess many merits, such as high efficiency and stability. Developing cost-effective, environmentally friendly, high-performance luminophores to achieve high-quality, full-spectrum, white lighting is of great importance to the construction and progress of WLEDs. In this work, solid-state, highly luminescent orange-emitting nanoclusters (MgCl2-Lys-Ag/Au NCs) were prepared via the salt-induced precipitation of Lys-Ag/Au NCs from solution, which showed a high absolute quantum yield of 44.5%. A cyan-emitting metal-organic framework (MOF)-like nanomaterial (named Fe@TAOH) was also prepared by the self-assembly of the coordination compound of Fe3+ and TAOH acted upon by H3PO4 via H-bonding and π-π stacking interactions, which showed an emission peak at 485 nm and an absolute quantum yield of 21.7%. The potential application of the two facile-synthesis, low toxicity, and highly luminescent materials in WLEDs was investigated. The WLEDs was constructed by coating powdered Fe@TAOH and MgCl2-Lys-Ag/Au NCs samples on commercial GaN LED chip with 365 nm emissions, and it exhibited acceptable white light characteristics with a CIE color coordinates and a color rendering index (CRI) of (0.28, 0.34) and 79.6, respectively, implying good prospects in the field of WLEDs.
Star-shaped small molecules have attracted great attention for organic solar cells (OSCs) because they have three-dimensional charge-transport characteristics, strong light absorption capacities and easily tunable energy levels. Herein, three- and four-armed star-shaped small molecule donors, namely BDT-3Th and BDT-4Th, respectively, have been successfully designed and synthesized, which used benzodithiophene (BDT) as the central unit. The two star-shaped intermediates (2a and 2b) could be simultaneously obtained by one-step of Suzuki coupling, and 1, 2-dimethoxyethane played a key role in the Suzuki coupling. Both of them have excellent thermal stability, good solubility and broad absorption. Four-armed BDT-4Th shows a slightly higher extinction coefficient, a deeper HOMO energy level and an obviously better phase separation morphology when blended with Y6 than three-armed BDT-3Th. As a result, increased power conversion efficiency (PCE) of 5.83% is obtained in the BDT-4Th: Y6-based OSC devices, which is obviously higher than that of the BDT-3Th: Y6-based devices (PCE = 3.78%). To the best of our knowledge, this is the highest PCE among the BDT-based star-shaped donors-based OSCs. This result provides an effective strategy to obtain star-shaped small molecule donor materials for high efficient organic solar cells.
Colorimetric and fluorescent probes have emerged as a potent tool for pH sensing due to easy operation and high sensitivity. However, most of the existing bimodal probes require complicated synthesis, which greatly limits their wide applications. Herein, a simple fluorescent dye (called BFCUR) featuring a D-π-A-π-D conjugated system was developed from the natural polyphenol curcumin (CUR). BFCUR exhibited significant red-shift in UV absorption and fluorescence emission as pH increased because of the deprotonation of the phenolic hydroxyl groups, which resulted in the enhanced intramolecular charge transfer (ICT). The ratiometric pH detection of BFCUR was achieved with remarkable accuracy by monitoring both the absorbance ratio A500/A650 and the fluorescence intensity ratio I622/I743 under various pH values. In addition, the clear color changes of BFCUR under different pH conditions were visible, which enabled BFCUR to be used in test strips for rapid, visual pH detection. Moreover, BFCUR exhibited low cytotoxicity, and was successfully applied for intracellular pH detection, where the fluorescence intensity was linearly related to pH value. This study highlighted the great potential of CUR-derived BFCUR as colorimetric and fluorescent probes for ratiometric-pH sensing and cell imaging.
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