Two birds one stone: β-fluoropyrrolyl-cysteine SNAr chemistry enabling functional porphyrin bioconjugation

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 S_NAr 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.     

有机催化吲哚碳环上的不对称Friedel⁃Crafts烷基化反应

将金鸡纳碱衍生物双功能催化剂用于有机催化羟基吲哚与靛红的不对称Friedel-Crafts反应, 筛选出最佳反应条件: 催化剂为5%(摩尔分数)6′-脱甲基奎尼丁(1b), 溶剂为四氢呋喃, 反应温度 0 ℃. 以67%~91%的产率和最高达97%的对映选择性获得了苯环上取代的羟基烷基化产品. 拓宽了该反应的催化剂类型和底物范围.     

神光-Ⅲ主机装置MJ级能源系统研制现状

介绍了神光-Ⅲ主机装置能源系统的功能要求、组成结构和设计方法,以及关键单元器件的功能要求和设计方法。该系统是片状放大器系统的重要组成部分,由6个束组共108套最大储能为1.2 MJ的能源模块组成,总储能达到110 MJ（最大130 MJ）。每套模块产生一个脉宽610 s(10 %峰值)的电流脉冲,驱动10组、共20支氙灯,为片状放大器提供泵浦能量,峰值电流为0.25 MA。目前投入试运行的36套能源模块的各项电气性能指标满足设计要求,能确保片状放大器小信号增益系数达到5.0%/cm,为片状放大器提供足够的泵浦能量,满足激光器的能量需求。     

初始模型对含噪动态光散射数据正则化反演结果的影响

分别采用最小模型矩阵、最平坦模型矩阵、最光滑模型矩阵作为初始化模型,对加入5种不同水平随机噪声的90 nm窄单峰、90 nm宽单峰和250 nm窄单峰、250 nm宽单峰颗粒体系的模拟分布进行了正则化反演,并对反演结果进行比较。结果表明：当噪声水平为0时,正则化初始模型的选择对反演结果没有明显影响。随着噪声水平的增加,采用三种初始化模型反演得到的峰值误差和粒度分布误差都随之变大,但采用最平坦模型和最光滑模型反演得到的峰值和粒度分布误差明显小于采用最小初始模型的反演误差。当噪声水平大于0.01时,选择最平坦初始模型获得的粒度分布结果优于采用最光滑初始模型和最小初始模型获得的结果,而采用最光滑初始模型反演得到的峰值优于最平坦初始模型和最小初始模型的反演峰值。因此,采用正则化算法处理含噪动态光散射数据时,为得到最优的粒度分布信息,宜采用最平坦初始模型,若需要获取最准确的峰值信息,则应选择最光滑初始模型。     

Highly Effective Proton-Conduction Matrix-Mixed Membrane Derived from an -SO3H Functionalized Polyamide

Developing a low-cost and effective proton-conductive electrolyte to meet the requirements of the large-scale manufacturing of proton exchange membrane (PEM) fuel cells is of great significance in progressing towards the upcoming “hydrogen economy” society. Herein, utilizing the one-pot acylation polymeric combination of acyl chloride and amine precursors, a polyamide with in-built -SO₃H moieties (PA-PhSO₃H) was facilely synthesized. Characterization shows that it possesses a porous feature and a high stability at the practical operating conditions of PEM fuel cells. Investigations of electrochemical impedance spectroscopy (EIS) measurements revealed that the fabricated PA-PhSO₃H displays a proton conductivity of up to 8.85 × 10⁻² S·cm⁻¹ at 353 K under 98% relative humidity (RH), which is more than two orders of magnitude higher than that of its -SO₃H-free analogue, PA-Ph (6.30 × 10⁻⁴ S·cm⁻¹), under the same conditions. Therefore, matrix-mixed membranes were fabricated by mixing with polyacrylonitrile (PAN) in different ratios, and the EIS analyses revealed that its proton conductivity can reach up to 4.90 × 10⁻² S·cm⁻¹ at 353 K and a 98% relative humidity (RH) when the weight ratio of PA-PhSO₃H:PAN is 3:1 (labeled as PA-PhSO₃H-PAN (3:1)), the value of which is even comparable with those of commercial-available electrolytes being used in PEM fuel cells. Additionally, continuous tests showed that PA-PhSO₃H-PAN (3:1) possesses a long-life reusability. This work demonstrates, using the simple acylation reaction with the sulfonated module as precursor, that low-cost and highly effective proton-conductive electrolytes for PEM fuel cells can be facilely achieved.     

THE GROWTH AND BOREL POINTS OF RANDOM ALGEBROID FUNCTIONS IN THE UNIT DISC

In this paper,we construct k-valued random analytic algebroid functions for the first time.By combining the properties of random series,we study the growth and ...     

Weaving 3D highly conductive hierarchically interconnected nanoporous web by threading MOF crystals onto multi walled carbon nanotubes for high performance Li-Se battery

Lithium-selenium (Li-Se) battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed pol...     

Multi-Interactions in Ionic Liquids for Natural Product Extraction

Natural products with a variety of pharmacological effects are important sources for commercial drugs, and it is very crucial to develop effective techniques to selectively extract and isolate bioactive natural components from the plants against the background of sustainable development. Ionic liquids (ILs) are a kind of designable material with unique physicochemical properties, including good thermal stability, negligible vapor pressure, good solvation ability, etc. ILs have already been used in pharmaceuticals for extraction, purification, drug delivery, etc. It has been reported that multi-interactions, like hydrogen bonding, hydrophobic interactions, play important roles in the extraction of bioactive components from the plants. In this review, recent progress in the understanding of scientific essence of hydrogen bonding, the special interaction, in ILs was summarized. The extraction of various natural products, one important area in pharmaceutical, by conventional and functional ILs as well as the specific roles of multi-interactions in this process were also reviewed. Moreover, problems existing in bioactive compound extraction by ILs and the future developing trends of this area are given, which might be helpful for scientists, especially beginners, in this field.     

Amorphous Manganese–Cobalt Nanosheets as Efficient Catalysts for Hydrogen Evolution Reaction (HER)

Catalysis Surveys from Asia - A facile and efficient electrocatalyst for hydrogen evolution reaction (HER) to produce hydrogen is very important for future energy. In this paper, amorphous...     

Synthesis and characterization of biodegradable amphiphilic ABC Y‐shaped miktoarm terpolymer by click chemistry for drug delivery

Biodegradable amphiphilic ABC Y‐shaped triblock copolymer (MPBC) containing PEG, PBLA, and PCL segments was synthesized via the combination of enzymatic ring‐opening polymerization (ROP) of epsilon‐caprolactone, ROP of BLA‐N‐carboxyanhydride and click chemistry, where PEG, PBLA, and PCL are poly(ethylene glycol), poly(benzyl‐l ‐aspartate), and polycaprolactone, respectively. Propynylamine was employed as ROP initiator for the preparation of alkynyl‐terminated PBLA and methyloxy‐PEG with hydroxyl and azide groups at the chain‐end was used as enzymatic ROP initiator for synthesis of monoazido‐midfunctionalized block copolymer mPEG‐b‐PCL. The subsequent click reaction led to the formation of Y‐shaped asymmetric heteroarm terpolymer MPBC. The polymer structures were characterized by different analyses. The MPBC terpolymer self‐assembled into micelles and physically encapsulated drug doxorubicin (DOX) to form DOX‐loaded micelles, which showed good stability and slow drug release. In vitro cytotoxicity study indicated that the MPBC micelles were nontoxic and the DOX‐loaded micelles displayed obvious anticancer activity similar to free DOX against HeLa cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3346–3355