Photosynthetic Fixation of CO2 in Alkenes by Heterogeneous Photoredox Catalysis with Visible Light

Light-driven fixation of CO₂ in organics has emerged as an appealing alternative for the synthesis of value-added fine chemicals. Challenges remain in the transformation of CO₂ as well as product selectivity due to its thermodynamic stability and kinetic inertness. Here we develop a boron carbonitride (BCN) with the abundant terminal B/N defects around the mesoporous walls, which essentially enhances surface active sites as well as charge transfer kinetics, boosting the overall rate of CO₂ adsorption and activation. In this protocol, anti-Markovnikov hydrocarboxylation of alkenes with CO₂ to an extended carbon chain is achieved with good functional group tolerance and specific regioselectivity under visible-light irradiation. The mechanistic studies demonstrate the formation of CO₂ radical anion intermediate on defective boron carbonitride, leading to the anti-Markovnikov carboxylation. Gram-scale reaction, late-stage carboxylation of natural products and synthesis of anti-diabetic GPR40 agonists reveal the utility of this method. This study sheds new insight on the design and application of metal-free semiconductors for the conversion of CO₂ in an atom-economic and sustainable manner.     

Atomically Dispersed Iron Regulating Electronic Structure of Iron Atom Clusters for Electrocatalytic H2O2 Production and Biomass Upgrading

The integration of highly active single atoms (SAs) and atom clusters (ACs) into an electrocatalyst is critically important for high-efficiency two-electron oxygen reduction reaction (2e⁻ ORR) to hydrogen peroxide (H₂O₂). Here we report a tandem impregnation-pyrolysis-etching strategy to fabricate the oxygen-coordinated Fe SAs and ACs anchored on bacterial cellulose-derived carbon (BCC) (FeSAs/ACs-BCC). As the electrocatalyst, FeSAs/ACs-BCC exhibits superior electrocatalytic activity and selectivity toward 2e⁻ ORR, affording an onset potential of 0.78 V (vs. RHE) and a high H₂O₂ selectivity of 96.5 % in 0.1 M KOH. In a flow cell reactor, the FeSAs/ACs-BCC also achieves high-efficiency H₂O₂ production with a yield rate of 12.51±0.18 mol g_cat⁻¹ h⁻¹ and a faradaic efficiency of 89.4 %±1.3 % at 150 mA cm⁻². Additionally, the feasibility of coupling the produced H₂O₂ and electro-Fenton process for the valorization of ethylene glycol was explored in detail. The theoretical calculations uncover that the oxygen-coordinated Fe SAs effectively regulate the electronic structure of Fe ACs which are the 2e⁻ ORR active sites, resulting in the optimal binding strength of *OOH intermediate for high-efficiency H₂O₂ production.     

One-Pot Synthesis of N-Benzyl/Allyl-N-phenyl-2-benzothiazolamines from 1-(2-Iodophenyl)-3-phenylthioureas and Benzyl/Allyl Halides

A facile method for the copper-catalyzed synthesis of N-benzyl-N-phenyl-2-benzothiazolamines was explored. In the presence of CuI, N-phenylbenzothiazolamines was in situ generated from substituted 1-(2-iodophenyl)-3-phenylthioureas, which susequently underwent coupling with benzyl/allyl halides to give the desired N-benzyl/allyl-N-phenyl-2-benzothiazolamines fluently in a one-pot manner. The protocol features easy performance, easily available materials, good yield and broad substrates scope, showing potential synthetic value for the preparation of a variety of biologically or pharmaceutically active compounds.     

Human Albumin-Based Hydrogels for Their Potential Xeno-Free Microneedle Applications

Nowadays, hydrogels-based microneedles (MNs) have attracted a great interest owing to their outstanding qualities for biomedical applications. For the fabrication of hydrogels-based microneedles as tissue engineering scaffolds and drug delivery carriers, various biomaterials have been tested. They are required to feature tunable physiochemical properties, biodegradability, biocompatibility, nonimmunogenicity, high drug loading capacity, and sustained drug release. Among biomaterials, human proteins are the most ideal biomaterials for fabrication of hydrogels-based MNs; however, they are mechanically weak and poorly processible. To the best of the knowledge, there are no reports of xeno-free human protein-based MNs so far. Here, human albumin-based hydrogels and microneedles for tissue engineering and drug delivery by using relatively new processible human serum albumin methacryloyl (HSAMA) are engineered. The resultant HSAMA hydrogels display tunable mechanical properties, biodegradability, and good biocompatibility. Moreover, the xeno-free HSAMA microneedles display a sustained drug release profile and significant mechanical strength to penetrate the model skin. In vitro, they also show good biocompatibility and anticancer efficacy. Sustainable processible human albumin-based biomaterials may be employed as a xeno-free platform in vivo for tissue engineering and drug delivery in clinical trials in the future.     

Fluorous Tagged Peptides for Intracellular Delivery and Biomedical Imaging

Fluorous tagged peptides have shown promising features for biomedical applications such as drug delivery and multimodal imaging. The bioconjugation of fluoroalkyl ligands onto cargo peptides greatly enhances their proteolytic stability and membrane penetration via a proposed “fluorine effect”. The tagged peptides also efficiently deliver other biomolecules such as DNA and siRNA into cells via a co-assembly strategy. The fluoroalkyl chains on peptides with antifouling properties enable efficient gene delivery in the presence of serum proteins. Besides intracellular biomolecule delivery, the amphiphilic peptides can be used to stabilized perfluorocarbon-filled microbubbles for ultrasound imaging. The fluorine nucleus on fluoroalkyls provides intrinsic probes for background-free magnetic resonance imaging. Labeling of fluorous tags with radionuclide ¹⁸F also allows tracing the biodistribution of peptides via positron emission tomography imaging. This mini-review will discuss properties and mechanism of the fluorous tagged peptides in these applications.     

基于机器学习的直接电离质谱爆炸物检测方法

直接电离质谱系统在现场快速检测中的应用日益广泛,主要用于爆炸物、毒品、食品添加剂等的检测。然而,直接电离质谱系统中质谱信号波动大且同一浓度样品峰强呈现对数正态分布,严重影响了检出限附近低浓度样品的检测准确性。该研究将乙酰水杨酸(115个样品)作为爆炸物模拟物,利用介质阻挡放电离子源与质谱系统,研究了基于机器学习的直接电离质谱数据预处理和分类算法,以提高低浓度样品的检测准确率。对两种浓度为1 ng/mL的常见爆炸物样本(三硝基甲苯和硝酸铵分别为110、90个)及空白对照样本(366个)开展了应用实验。结果表明,与传统提取离子流方法和高斯混合模型方法相比,采用随机森林算法可将F_score从0.74、0.89提升至0.96,显著提高了检测准确率,且单个样本数据分析时间远少于0.1 s,满足实时检测需求。     

1H NMR Reassignment for Z/E-Benzomalvins B and Absolute Configuration of Benzomalvin C

Chemistry of Natural Compounds - Benzomalvins B, C, and E (1, 2, and 3) were simultaneously obtained from the marine fungus Aspergillus sp. isolated from the soft coral Sinularia sp., collected...     

Ni(OH)2修饰的三聚氰胺泡沫用于可压缩超级电容器电极

通过化学镀和电化学镀的方法制备了一种Ni(OH)₂电化学活性材料修饰三聚氰胺泡沫(MF)可压缩骨架的超级电容器电极材料MF/Ni(OH)₂。MF/Ni(OH)₂可压缩电极材料表现出最佳的电容性能,例如循环稳定性(即使在40 mA/cm^-3的电流密度下经过2000次充放电循环后,可压缩电极仍能保持90.63%的初始电容)和可压缩稳定性(即使在压缩率为50%时,仍具有97.88%的电容保持率)。层状可压缩超级电容器由MF/Ni(OH)₂弹性材料作为阳极,镍/碳(Ni/C)为阴极以及实验室中常用的滤纸作隔膜材料组成。这种超级电容器装置在不同的压缩下表现出良好的电化学性能和优异的压缩稳定性。最后,使用可压缩的超级电容器来点亮LED灯,以展示其在柔性电子设备中的应用。这些优化的电化学和机械性能表明MF/Ni(OH)₂可作为可压缩超级电容器的应用中的候选电极。     

微流控纸芯片在环境分析检测中的应用

近年来,微流控纸芯片由于低成本、便携化、检测快等优点,在需要快速检测的环境分析领域中展现出了巨大的应用前景。该综述从微流控纸芯片在环境分析中的应用角度,总结归纳了微流控纸芯片在环境分析中的最新研究进展,并展望了其在未来的发展趋势与挑战。论文内容引用150余篇源于科学引文索引(SCI)与中文核心期刊中的相关论文。该综述包括微流控纸芯片在环境检测中的优势与制造方法介绍;电化学法、荧光法、比色法、表面增强拉曼法、集成传感法等基于纸芯片的先进分析方法介绍;根据环境分析目标物种类,如重金属离子、营养盐、农药、微生物、抗生素以及其他污染物等,对纸芯片的最新应用现状进行了举例评述;基于微流控纸芯片的环境分析研究的未来发展趋势和前景展望。通过综述近期相关研究,表明微流控纸芯片从提出至今虽然只有十几年的发展历程,但其在环境分析研究中的发展却十分迅速。微流控纸芯片可以根据不同的环境条件和检测要求灵活选择制作与分析方法,实现最佳的检测效果。但是微流控纸芯片也面临一些挑战,如纸张机械强度不足、流体控制程度不佳等问题。这些问题指出了微流控纸芯片在环境检测领域的发展趋势,相信随着不断深入的研究,纸芯片将会在未来的环境分析中发挥更大作用。     

碳点的性质及其在生物传感器领域的应用

碳点(carbon dots,CDs)作为一种具有优良生物相容性、低毒性和表面功能可调的新型碳基纳米材料,在生物传感领域具有极大的应用潜力.本文对碳点的生物效应、发光性质及其发光机理进行了简述,并根据传感机制的不同,将CDs在生物传感领域的应用分为荧光(fluorescence,FL)传感器、电致发光(electrochemiluminescence,ECL)传感器以及化学发光(chemiluminescence,CL)传感器三类进行综述.最后分析了CDs目前在生物传感器领域应用中存在的问题,并对其发展进行了展望.