Iron-mediated AGET ATRP of styrene and methyl methacrylate using ascorbic acid sodium salt as reducing agent

Atom transfer radical polymerization of styrene(St) and methyl methacrylate(MMA) in bulk and in different solvents using activators generated by electron transfer(AGET ATRP) were investigated in the presence of a limited amount of air using FeCl3·6H2O as the catalyst, ascorbic acid sodium salt(AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide(TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene: 1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.     

Investigation of Hydrolysis in Poly（ethylene terephthalate） by FTIR-ATR

The hydrothermal aging of poly(ethylene terephthalate)(PET) was investigated at 70 95 °C. A new method to investigate the hydrolysis degree of PET by Fourier transform infrared spectroscopy(FTIR) was proposed. The spectra during the hydrothermal aging were measured using attenuated total reflection accessory(ATR). Peak resolving of carbonyl regions was performed, and the ratio of two groups of bands representing carboxylic acids and esters respectively were calculated to show the hydrolysis degree of ester groups in PET. The acid/ester ratio shows exactly the same trend as the average chain scission number per unit mass at various temperatures and thus can be used as a parameter to characterize the hydrolysis and random chain scission of PET. This method related to the hydrolysis mechanism directly, is simple, fast and convenient compared to the traditional methods such as viscometry, end-group titration and size exclusion chromatography(SEC). It may also be useful in hydrolysis characterization of other polyesters.     

Microstructure characterization of short-chain branching polyethylene with differential scanning calorimetry and successive selfnucleation/annealing thermal fractionation

A series of the copolymers of ethylene with 1-hexene(M1–M9) synthesized by metallocene catalyst Et[Ind]2ZrCl2/MAO was studied by differential scanning calorimetry and successive self-nucleation and annealing(SSA) thermal fractionation. The distribution of methylene sequence length(MSL) in the different copolymers was determined using the SSA method. The comonomer contents of samples M4 and M5 are 2.04 mol% and 2.78 mol%, respectively. Both M4 and M5 have low comonomer content and their MSL distribution profiles exhibit a monotonous increase trend with their MSL. The longest MSL of M5 is 167, and its corresponding molar percent is 43.95%, which is higher than that of M4. Moreover, the melting temperature(Tm) of M5 is also higher than that of M4. The comonomer contents of samples M7, M8, and M9 are 8.73 mol%, 14.18 mol% and 15.05 mol%, respectively. M7, M8, and M9 have high comonomer contents, and their MSL distribution profiles display unimodality. M7 has a lower peak value of 33 and a narrow MSL distribution, resulting in a Tm lower than that of M8 and M9. The MSL and its distribution are also key points that influence the melting behavior of copolymers. Sometimes, MSL and its distribution of copolymers have a greater impact on it than the total comonomer contents, which is different from traditional views.     

两种异马来二氰基二硫烯镍(II)-取代苄基喹啉鎓盐的制备及其光谱性质和晶体结构

以甲醇为溶剂,将异马来二氰基二硫烯酸钾[K2(i-mnt)]和六水氯化镍分别与溴化4-溴苄基喹啉盐([4-BrBzQl]Br)或溴化4-硝基苄基喹啉盐([4-NO2BzQl]Br)直接反应,得到两种新的离子对配合物[4-BrBzQl]2[Ni(i-mnt)2](1)和[4-NO2BzQl]2[Ni(i-mnt)2](2);测定了其红外光谱和紫外-可见光谱,并利用X射线衍射表征了配合物1的晶体结构.结果表明,配合物[4-BrBzQl]2[Ni(i-mnt)2]为三斜晶系,P-1空间群,其每个不对称单元含半个[Ni(i-mnt)2]2-阴离子和1个[4-BrBzQl]+阳离子,晶体中的阴、阳离子通过静电作用和C-H…S、C-H…N氢键作用形成网络结构.     

CM⁃Phos配体在钯催化交叉偶联反应中的应用

本文综合评述了近年来2-[2-(二环己膦基)苯基]-1-甲基-1H-吲哚(CM-Phos)膦配体及其衍生物在钯催化的交叉偶联反应中的应用, 主要根据不同种类的交叉偶联反应进行系统性分述, 并对该领域的发展前景进行了展望.     

氧化石墨烯调控钼酸铋在可见光下选择性光催化降解环境水中的抗生素

以氧化石墨烯(GO)作为增强光催化剂活性的调节剂, 采用一步水热法制备钼酸铋/氧化石墨烯(Bi₂MoO₆/GO)异质结光催化剂, 其可见光响应拓展至570 nm, 带隙能降至2.56 eV. 当m_Bi2MoO6/m_GO=100∶1时, Bi₂MoO₆/GO(100∶1)光催化剂在可见光的辐射下, 对水溶液中四环素和喹诺酮类抗生素选择性的高效催化降解去除能力为Bi₂MoO₆的2.1倍. Bi₂MoO₆/GO(100∶1)光催化剂活性的提高依赖于范德华力作用下的二维Bi₂MoO₆纳米片-二维GO纳米片界面的紧密接触. 有效的界面接触改善了光生电子的转移和光生载流子的分离. 自由基清除实验结果表明, ?OH起主要作用. 结合高效液相色谱-质谱(HPLC-MS)法对降解产物的分析, 提出了不同光催化剂催化降解恩诺沙星具有相似的降解途径和降解产物.     

Unprecedented Kinetic Inertness for a Mn2+‐Bispidine Chelate: A Novel Structural Entry for Mn2+‐Based Imaging Agents

The search for more biocompatible alternatives to Gd³⁺‐based MRI agents, and the interest in ⁵²Mn for PET imaging call for ligands that form inert Mn²⁺ chelates. Given the labile nature of Mn²⁺, high inertness is challenging to achieve. The strongly preorganized structure of the 2,4‐pyridyl‐disubstituted bispidol ligand L₁ endows its Mn²⁺ complex with exceptional kinetic inertness. Indeed, MnL₁ did not show any dissociation for 140 days in the presence of 50 equiv. of Zn²⁺ (37 °C, pH 6), while recently reported potential MRI agents MnPyC3A and MnPC2A‐EA have dissociation half‐lives of 0.285 h and 54.4 h under similar conditions. In addition, the relaxivity of MnL₁ (4.28 mm ^?1 s^?1 at 25 °C, 20 MHz) is remarkable for a monohydrated, small Mn²⁺ chelate. In vivo MRI experiments in mice and determination of the tissue Mn content evidence rapid renal clearance of MnL₁. Additionally, L₁ could be radiolabeled with ⁵²Mn and the complex revealed good stability in biological media.     

Synthesis and relaxivity of polyamide paramagnetic metal complexes for magnetic resonance imaging

A new class of paramagnetic macromolecular magnetic resonance imaging contrast agents has been developed. Eight new polyamide ligands were synthesized by copolymerization of ethylenediaminetetraacetic acid dianhydride or diethylenetriaminepentaacetic acid dianhydride and diamine monomers. Their gadolinium(III), manganese(II) and iron(III) complexes were also synthesized. All polyamide ligands and metal complexes were characterized by ¹H nuclear magnetic resonance, infrared spectra and elemental analyses. Relaxivity studies showed that the polyamide paramagnetic metal complexes had obviously higher relaxation effectiveness as compared to corresponding simple monomeric paramagnetic metal complexes.     

带有双X型铁心框架的超导MRI磁体的设计

文中对带有双X型铁心框架的MR I用高温和低温超导磁体的设计进行了介绍,包括项目的市场需求、磁体的基本参数和系统热负荷的预设计结果等。     

基于级联卷积神经网络的前列腺磁共振图像分类

针对深度学习训练成本高,以及基于磁共振图像的前列腺癌临床诊断需要大量医学常识且极为耗时的问题,本文提出了一种基于级联卷积神经网络（Convolutional Neural Network,CNN）和磁共振图像的前列腺癌（Prostate Cancer,PCa）自动分类诊断方法,该网络以Faster-RCNN作为前网络,对前列腺区域进行提取分割,用于排除前列腺附近组织器官的干扰;以基于ResNet改进的网络结构CNN40_bottleneck作为后网络,用于对前列腺区域病变进行分类.后网络由瓶颈结构串联组成,其中使用批量标准化（Batch Normalization,BN）、全局平均池化（Global Average Pooling,GAP）进行优化.实验结果证明,本文方法对前列腺癌诊断结果较好,而且缩减了训练时间和参数量,有效降低了训练成本.