An Activatable Polymeric Reporter for Near-Infrared Fluorescent and Photoacoustic Imaging of Invasive Cancer

Discriminative detection of invasive and noninvasive breast cancers is crucial for their effective treatment and prognosis. However, activatable probes able to do so in vivo are rare. Herein, we report an activatable polymeric reporter (P-Dex) that specifically turns on near-infrared (NIR) fluorescent and photoacoustic (PA) signals in response to the urokinase-type plasminogen activator (uPA) overexpressed in invasive breast cancer. P-Dex has a renal-clearable dextran backbone that is linked with a NIR dye caged with an uPA-cleavable peptide substrate. Such a molecular design allows P-Dex to passively target tumors, activate NIR fluorescence and PA signals to effectively distinguish invasive MDA-MB-231 breast cancer from noninvasive MCF-7 breast cancer, and ultimately undergo renal clearance to minimize the toxicity potential. Thus, this polymeric reporter holds great promise for the early detection of malignant breast cancer.     

PbTiO3/SrTiO3(010)异质界面上的周期性失配位错及电子富集

It is important to determine the effects of misfit dislocations and other defects on the domain structure, ferroelectricity, conductivity, and other physical properties of ferroelectric thin films to understand their ferroelectric and piezoelectric behaviors. Much attention has been given to ferroelectric PbTiO₃/SrTiO₃ or PbZr_0.2Ti_0.8O₃/SrTiO₃ heterointerfaces, at which improper ferroelectricity, a spin-polarized two-dimensional electron gas, and other physical phenomena have been found. However, those heterointerfaces were all (001) planes, and there has been no experimental studies on the growth of (010) PbTiO₃/SrTiO₃ heterointerface due to the 6.4% misfit between two materials. In this study, we selected an atomically flat (010) PbTiO₃/SrTiO₃ heterointerface grown using a two-step hydrothermal method as the research subject, and this is the first experimental report on that interface. Interfacial dislocations can play a significant role in causing dramatic changes in the Curie temperature and polarization distribution near the dislocation cores, especially when the size of a ferroelectric thin film is scaled down to the nanoscale. The results of previous studies on the effects of interfacial dislocations on the physical properties of ferroelectric thin films have been contradictory. Thus, this issue needs to be explored more deeply in the future. This study used aberration corrected scanning transmission electron microscopy (STEM) to study the atomic structure of a (010) PbTiO₃/SrTiO₃ heterointerface and found periodic misfit dislocations with a Burgers vector of a[001]. The extra planes at the dislocation cores could relieve the misfit strain between the two materials in the [001] direction and thus allowed the growth of such an atomically sharp heterointerface. Moreover, monochromated electron energy-loss spectroscopy with an atomic scale spatial resolution and high energy resolution was used to explore the charge distribution near the periodic misfit dislocation cores. The fine structure of the Ti L edge was quantitatively analyzed by linearly fitting the experimental spectra recorded at various locations near and at the misfit dislocation cores with the Ti³⁺ and Ti⁴⁺ reference spectra. Therefore, the accurate valence change of Ti could be determined, which corresponded to the charge distribution. The probable existence of an aggregation of electrons was found near the a[001] dislocation cores, and the density of the electrons calculated from the valence change was 0.26 electrons per unit cell. Based on an analysis of the fine structure of the oxygen K edge, it could be argued that the electrons aggregating at the dislocation cores came from the oxygen vacancies in the interior regions of the PbTiO₃. This aggregation of electrons will probably increase the electron conductivity along the dislocation line. The physics of two-dimensional charge distributions at oxide interfaces have been intensively studied, however, little attention had been given to the one-dimensional charge distribution. Therefore, the results of this study can stimulate research interest in exploring the influence of the interfacial dislocations on the physics of ferroelectric heterointerfaces.     

Two Novel Coordination Polymers with(6,3) Topology Constructed by an Imidazole-containing Isophthalic Ligand:Syntheses,Structures and Luminescence Properties

Two novel coordination polymers,[Zn(ImNIPA)(DMSO)]n(1)and[Cd(ImNIPA)(DMSO)]n(2)(H2ImNIPA=5-(6-(1H-imidazol-1-yl)-1,3-dioxo-1H-benzo[de]iso-quinolin-2(3H)-yl)isophthalic acid,DMSO=dimethylsulfoxide),were prepared under solvothermal conditions through the reactions of Zn^2+/Cd^2+ and a new imidazole-containing isophthalic ligand H2ImNIPA.The compounds were fully characterized by elemental analysis,FT-IR spectroscopy,powder X-ray diffraction analysis and X-ray single-crystal diffraction analysis.Both 1 and 2 are two-dimensional(2D)coordination layers via the combination of 3-connected metal nodes and ImNIPA^2- linker,featuring(6,3)honeycomb-type topology.In addition,the 2D layers in the two compounds are further extended into 3D supramolecular frameworks via π-π stacking interactions.Finally,the thermal-stability and solid-state luminescence properties of them were also investigated.     

BiPO4/石墨烯光电极的制备及其光电催化性能（英文）

光电催化(PEC)氧化法是一种使用半导体电极材料在光和电的共同作用下处理水中有机污染的有效方法.在PEC工艺中,施加偏压不仅可以利用电催化对有机污染物进行降解,而且在偏压作用下,光生电子-空穴对能够得到有效的分离和传输,从而大大提高了机物污染物的去除速率.尽管PEC技术已经取得了许多重要的突破,但是能量转换效率仍然无法满足实际应用.因此,开发具有优异性能,良好稳定性和低成本的光电极材料是一项具有挑战性的研究工作.本文采用两步电沉积法制备了BiPO4纳米棒/还原氧化石墨烯/FTO复合光电极(BiPO4/r GO/FTO).电镜结果表明,电沉积制得的纳米棒状磷酸铋均匀负载在石墨烯纳米片层表面.采用甲基橙为模型体系,考察了复合光电极的光电催化活性.BiPO4/r GO/FTO复合电极的光电催化降解速率是BiPO4/FTO光电极的2.8倍,显示出优良的光电催化活性.实验进一步研究了工作电压和BiPO4沉积时间对甲基橙光电降解性能的影响.最佳的BiPO4沉积时间为45 min,最佳工作电压为1.2 V.捕获实验和ESR实验表明羟基自由基(·OH)和超氧化物自由基(·O2-)是该电极的主要活性物种.BiPO4/r GO/FTO复合电极经过四次循环实验后其降解甲基橙效率保持不变,显示出高稳定性,采用光电流,交流阻抗及其荧光测试对其光催化机理进行推测.结果表明该复合光电极具有高PEC活性的主要原因是:石墨烯的引入加快了BiPO4的电子空穴的分离,拓宽了石墨烯的可见光吸收范围;同时,石墨烯诱导产生的BiPO4混合相也进一步促进了光生电子空穴的分离,提高了光电降解活性.     

Regulating Gelation Time and Kinetics Analysis Based on the ARGET ATRP Mechanism

A novel activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) initiation system composing of an initiator sodium chloroacetate, a catalyst ferric chloride, and a reducing agent ascorbic acid was developed to improve the gelation time of the in situ crosslinked polymer system. The kinetics of polymerization of acrylamide showed features of a living/controlled process in which the concentrations of the growing radicals [P·] are kept constant throughout the polymerization process. Compared with conventional potassium persulfate initiators, the gelation time of the in situ crosslinked polymer system can be improved to 40 h or even longer using the ARGET ATRP initiation system at 80 °C due to the low radical concentration and slow polymerization reaction. Core flooding test showed that the ARGET ATRP initiating system developed could initiate the polymerization reaction of the in situ crosslinked polymer system in the core. However, the gelation time was extended in comparison to that of the result obtained in the bottle, resulting from the dilution and adsorption of ARGET ATRP components during the injection process. The research expands the application field of the ARGET ATRP principle and has a promising prospect on controlling the gelation time of the in situ crosslinked polymer system. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 519–527     

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)†

A Cu(I)‐catalyzed three‐component reaction of terminal enynals/enynones, diazo compounds, and alkenes has been developed. With this method, a series of oxabicyclo[2.2.2]octanes were effectively synthesized in high yields under mild reaction conditions. This transformation is proposed to proceed through trapping of the cyclic vinyl‐o‐quinodimethanes (vinyl‐o‐QDMs) species, which were generated from terminal enynals/enynones and diazo compounds by alkenes. The obvious advantages of wide substrate scopes, mild reaction conditions, and high seteroselectivity and atom efficiency make this reaction highly appealing for construction of highly rigid [2.2.2]octane skeleton.     

基于蓝墨云班课的“物理化学实验”微课设计与应用*

为解决物理化学实验教学中存在的问题,以蓝墨云班课为教学平台,利用微课资源,采用翻转课堂和传统教学有机结合的教学方式,进行教学改革,详细介绍了物理化学实验微课的设计、应用及效果分析。教学实践表明,教改后的教学模式有效激发了学生的学习积极性,提升了教学效率和效果。     

石墨相氮化碳/蒙脱石复合材料的制备及其可见光催化性能

为提高石墨相氮化碳(g-C₃N₄)对可见光的利用率及光催化效率,采用热聚合与直接负载等方法,将g-C₃N₄负载于蒙脱石表面,制备了g-C₃N₄/蒙脱石复合光催化材料,其结构经SEM, FT-IR及XRD表征。以罗丹明B(RhB)为目标污染物,研究了不同负载量g-C₃N₄/蒙脱石复合光催化剂的可见光催化性能。并分别以对苯醌、碘化钾和异丙醇为自由基捕获剂,研究了复合材料的光催化机理。结果表明：当g-C₃N₄的质量分数为83%(CN/M-83%)时,RhB经可见光照射1 h后,降解率达到99.2%。光催化速率常数为纯g-C₃N₄光催化速率常数的3.2倍。     

Demystifying terms for understanding bioelectrochemical systems towards sustainable wastewater treatment

Bioelectrochemical systems (BESs) have been intensively studied in the past decade, but precise understanding of BESs performance is hindered by unclear definition of several key parameters. Herein, we analyze and discuss three sets of terms about conversion efficiency, energy performance, and pilot scale. It is suggested that ‘Coulombic recovery’ can avoid the misleading results because of different organic removals, compared with ‘Coulombic efficiency.’ Power density is not a suitable term to describe energy performance of BESs, and energy production/consumption should be reported in the energy unit such as kWh. Pilot-scale BESs should meet several criteria, including hydraulic capacity, use of actual wastewater, non-laboratory condition, and long-term operation. Proper use of those terms is strongly encouraged and will be critically important to BESs research and development.     

选矿产品矿物自动分析的光片制备

基于扫描电子显微镜的矿物自动分析仪(Quantitative Evaluation of Minerals by Scanning Electronic Microscopy)、MLA(Mineral Liberation Analyser)和AMICS(Advanced Mineral Identification and Characterization System)可用于测定选矿产品中目的矿物的粒度和单体解离度,为确定合理的磨矿细度以及优化选矿工艺流程提供依据。环氧树脂光片的制备是矿物自动识别和测量的最关键的一环,其代表性直接关系到后续数据测量的准确性和真实性。对于金属矿产品来说,由于选矿产品中矿物颗粒粗细不均、密度差异较大,在环氧树脂胶结固化过程中矿物颗粒会产生明显的分异作用并互相黏连,造成分析结果失真。实验证明,把样品与晶质石墨混均,然后加入环氧树脂以及固化剂搅拌混合倒入圆柱状模具进行冷镶嵌,待样品固化后再沿圆柱体的纵向进行切割,并对其切割面进行粗磨、细磨、精磨以及抛光,就可以制备出样品分散性好、分布均匀、表面光滑平整的具有代表性的环氧树脂光片。