A Feasible and Quantitative Encoding Method for Microbeads with Multicolor Quantum Dots

Multicolor encoded beads were achieved by incorporating two color core-shell quantum dots (QDs) (CdSe/ZnS) to commercial polystyrene (PS) beads. By controlling the concentration ratios of the two quantum dots (QDs) in doping solutions, a series of codes with different intensity ratios were obtained. Based on the multiple encoded carboxylic modified polystyrene beads, fluorescent dyes labeled antibodies were distinguished successfully on the beads’ surface. It suggests that the encoded beads from this method have the practicability in biological applications and chemical analysis. Hai-Qiao Wang and Zhen-Li Huang authors contribute equally to this work     

金属相1T´ MoS2增强类石墨相C3N4的可见光催化性能

通过煅烧和静电自组装的方法制备了1T′ MoS₂超薄纳米片和类石墨烯相氮化碳(g-C₃N₄)纳米片的复合材料. 该材料在光催化实验中展现出6.24 μmol?g^?1?h^?1的产氢速率, 优于贵金属铂修饰的g-C₃N₄纳米片的性能(4.64 μmol?g^?1?h^?1). 此外, 该复合材料在光催化降解有机染料甲基橙的实验中表现出0.19 min^?1的催化速率, 而纯g-C₃N₄纳米片只有0.053 min^?1的催化速率. 材料光催化性能的提升可归结于1T′MoS₂ 和g-C₃N₄之间的协同效应, 包括光吸收的增强以及因1T′MoS₂优异电子导电性而得到的高效电荷分离.     

长链支化聚丙烯的非线性流变行为

通过大幅振荡剪切试验方法, 研究了长链支化聚丙烯的非线性流变学行为, 揭示了长链支化结构与非线性黏弹响应的关系. 利用傅里叶变换流变学方法得到试样的三次倍频相对振幅I_3/1与应变的标度关系, 用于界定线性聚丙烯和长链支化聚丙烯非线性流变行为的差异, 并定义了非线性系数来量度长链支化程度. 在高应变下, I_3/1与应变的变化关系可以进一步描述长链支化在非线性流场下的特性, 并得到了长链支化程度与其非线性响应之间的变化关系. 通过应力波的Lissajous曲线分解, 发现了环内和环间黏弹性的差异, 长链支化结构在大应变流场下的非线性黏弹性响应弱于线性结构, 支化程度越高非线性响应越弱.     

N-[2,6-二氯-4-(1,2,4-噁二唑-3-基)苯基]-2-甲氧基烟酰胺的合成、晶体结构及抗肿瘤活性研究

报道一种新型1,2,4-噁二唑衍生物,N-[2,6-二氯-4-(1,2,4-噁二唑-3-基)苯基]-2-甲氧基烟酰胺（C15H10Cl2N4O3）的合成,其结构通过1H NMR、13C NMR、HRMS以及X-射线单晶衍射进行表征。该晶体结构属于三斜晶系, P 1(—) 空间群,晶胞参数 a = 7.1291 (9), b = 8.4352 (10), c = 14.0021 (18) ?, α = 73.834 (3), β = 77.407 (3), γ = 70.019 (3)°, Mr = 366.18, V = 752.97 (16) ?3, Z = 2, Dc = 1.611 g/cm3, μ(MoKα) = 0.454 mm-1, F(000) = 372.0 , 晶体尺寸为 0.36 × 0.2 × 0.1 mm,Rint = 0.023。初步活性研究发现,该化合物对LoVo, A549, SK-BR-3, HeLa这四种肿瘤细胞株具有明显的抑制作用,尤其是对HeLa细胞的抑制活性与阳性药物5-氟尿嘧啶 (5-FU)相当。     

Reversibly self-assembled pH-responsive PEG-p(CL-g-TMC) polymersomes

Polymersomes have gained much interest within the biomedical field as drug delivery systems due to their ability to transport and protect cargo from the harsh environment inside the body. For an improved drug efficacy, control over cargo release is however also an important factor to take into account. An often employed method is to incorporate pH sensitive groups in the vesicle membrane, which induce disassembly and content release when the particles have reached a target site in the body with the appropriate pH, such as the acidic microenvironment of tumor tissue or the endosome. In this paper, biodegradable poly(ethylene glycol)-poly(caprolactone-gradient-trimethylene carbonate)-based polymeric vesicles have been developed with disassembly features at mild acidic conditions. Modifying the polymer backbone with imidazole moieties results in vesicle disassembly upon protonation due to the lowered pH. Furthermore, upon increasing the pH efficient re-assembly into vesicles is observed due to the switchable amphiphilic nature of the polymer. When this re-assembly process is conducted in presence of cargo, enhanced encapsulation is achieved. Furthermore, the potency of the polymeric system for future biomedical applications such as adjuvant delivery is demonstrated.     

MIL-53(Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

卤代苯胺是化学工业中重要的中间体,主要用于制造药物、聚合物、染料等含氮化学品,用多相金属催化剂催化卤代硝基芳烃加氢制备卤代苯胺是一种高效,绿色和可持续发展的生产工艺.该过程需要选择性加氢硝基基团,同时避免卤素基团的脱卤副反应发生.然而,化学选择性加氢存在巨大的挑战,难点在于催化剂的精准设计,一方面要求具备对硝基基团合适的加氢能力,另一方面要阻止对卤素基团的脱卤副反应发生.基于此,研制高效多相金属催化剂用于卤代硝基芳烃选择性加氢制备卤代苯胺反应引起了高度关注.近年来,单原子金属催化剂受到越来越多的关注,并在卤代硝基芳烃选择性加氢制备卤代苯胺反应中显现出极大的潜力.本文通过在金属有机骨架材料MIL-53(Al)自组装的过程中将金属Rh原位嫁接其骨架结构中,继而通过限域热解的方法制备了Rh@Al2O3@C单原子催化剂,其在间氯硝基苯(m-CNB)加氢制间氯苯胺(m-CAN)反应中显现了高效催化选择性.球差校正高角度环形暗场模式的透射电镜,CO作为探针分子的红外光谱和X射线光电子能谱等结果发现,Rh是以单原子的形式均匀的分布在Al2O3上并被无定型碳包覆,且Rh化学价态呈正价.而27Al固体核磁共振与密度泛函理论计算的结果则进一步确定Al2O3@C载体中存在的五配位的Al物种(AlV)是锚定Rh单原子的主要位点,AlV的不饱和的配位结构可以有效地稳定Rh单原子,对形成Rh位点的单原子分散至关重要.在间氯硝基苯选择性加氢制间氯苯胺反应中,与等体积浸渍法制备的Rh/C和Rh/γ-Al2O3纳米催化剂相比,Rh@Al2O3@C单原子催化剂表现出优异催化性能:其在313 K,氢气压力为20 bar的温和条件下转换频率(TOF)高达2317 molm-CNB·molRh-1·h-1,优于已报道的多相金属催化剂,是目前的最高值.此外,该催化剂展现出极佳的稳定性能,经过五次循环后,该催化剂对m-CAN的选择性仍旧保持在98％左右.Rh@Al2O3@C单原子催化剂的优异催化性能源自于金属单原子结构的形成对于金属位点电子结构的有效调节,进而调控催化剂加氢性能并实现对加氢脱卤副反应的抑制;与此同时,Rh@Al2O3@C催化剂增进了酸位点的可及性,从而促进了其串联步骤中包含的脱水反应的发生,进而有效提高催化剂的反应活性.     

基于氮杂Mn咔咯二维纳米材料的单原子Mn中心催化氧化烷烃制醇

咔咯是由四个吡咯共轭相连而形成的具有芳香性的新型卟啉类大环化合物,但咔咯分子中存在一个直接连结两个吡咯环的C?C键,与卟啉相比,仅仅是少了一个“meso”位置的C原子.因此,在结构上,咔咯含有三个“吡咯型”氮原子和一个“吡啶型”氮原子,当咔咯失去三个内氢原子后变成了三价阴离子,易与金属形成高价态的稳定配合物.氮杂咔咯是一种咔咯的meso位上的C被取代为N的咔咯衍生物.与正常的咔咯相比,它更易于与过渡金属形成稳定配合物.正是由于这些独特的结构特点,使其在金属催化、染料敏化太阳能电池、光敏剂、金属传感器、甚至在医学上都有很好的应用前景.金属有机大环均相催化剂的非均相化,是改进反应产物分离和实现催化剂循环使用的最简单有效方法之一.环境友好的Mn氮杂咔咯催化剂,在温和条件下可以利用氧气直接将有机底物氧化.本文选用Mn氮杂咔咯催化剂作为基本构建单元,通过理论计算,构建了一种新型的具有高催化活性的含Mn氮杂咔咯环结构单元的二维纳米催化材料.我们分别使用高斯软件(Gaussian 09)和维也纳从头算模拟软件包(VASP)对孤立分子和周期性体系进行结构优化以及性质的计算.在这种二维材料中,每一个Mn原子作为相对独立的金属单原子中心(SAC),保留了单环中Mn金属中心的高催化活性.在温和的光照条件下,Mn金属中心可以直接活化氧气生成类自由基[Mn]-O-O中心,随后[Mn]-O-O中心可以有效地通过夺取有机底物中的H和紧接着新生自由基的偶合反应,选择性氧化C?H键为C?OH键.另外,通过沿[Mn]-O-O反应轴施加不同强度的外电场,可对此二维纳米材料的催化反应活性进行精细调控.本文为实验上制备基于Mn氮杂咔咯的非均相催化剂以及单原子Mn基催化剂提供了理论依据.     

A Triple Crosslinking Design toward Epoxy Vitrimers and Carbon Fiber Composites of High Performance and Multi-shape Memory

It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances. Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer(MSMEV), which exhibits high mechanical properties,multi-shape memory property and malleability. The triple crosslinking network is formed by reacting diglycidyl ether of bisphenol F(DGEBF) with4-aminophenyl disulfide, γ-aminopropyltriethoxysilane(APTS) and poly(propylene glycol) bis(2-aminopropyl ether)(D2000). The triple crosslinking manifests triple functions: the disulfide bonds and the silyl ether linkages enable malleability of the epoxy network; the silyl ether linkages impart the network with high heterogeneity and broaden the glass transition region, leading to multi-shape memory property; a small amount of D2000 increases the modulus difference between the glassy and rubbery states, thereby improving the shape fixity ratio. Meanwhile,the high crosslinking density and rigid structure provide the MSMEV with high tensile strength and Young's modulus. Moreover, integrating carbon fibers and MSMEV results in shape memory composites. The superior mechanical properties of the composites and the recyclability of carbon fiber derived from the dissolvability of MSMEV make the composites hold great promise as structural materials in varied applications.     

Rapid and label-free classification of pathogens based on light scattering,reduced power spectral features and support vector machine

The rapid identification of pathogens is crucial in controlling the food quality and safety. The proposed system for the rapid and label-free identification of pathogens is based on the principle of laser scattering from the bacterial microbes. The clinical prototype consists of three parts: the laser beam, photodetectors, and the data acquisition system. The bacterial testing sample was mixed with 10 mL distilled water and placed inside the machine chamber. When the bacterial microbes pass by the laser beam, the scattering of light occurs due to variation in size, shape, and morphology. Due to this reason, different types of pathogens show their unique light scattering patterns. The photo-detectors were arranged at the surroundings of the sample at different angles to collect the scattered light. The photodetectors convert the scattered light intensity into a voltage waveform. The waveform features were acquired by using the power spectral characteristics, and the dimensionality of extracted features was reduced by applying minimal-redundancy-maximal-relevance criterion (mRMR). A support vector machine (SVM) classifier was developed by training the selected power spectral features for the classification of three different bacterial microbes. The resulting average identification accuracies of E. faecalis,E. coli and S. aureus were 99%, 87%, and 94%, respectively. The overall experimental results yield a higher accuracy of 93.6%, indicating that the proposed device has the potential for label-free identification of pathogens with simplicity, rapidity, and cost-effectiveness.     

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO₂ responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO₂,1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO₂ and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.