Novel Isatin-Schiff Base Cu (II) and Ni(II) Complexes. X-ray Crystal Structure of Bis[3-(4-hexylphenylimino)-1H-indol-2(3H)-one]-dichlorocopper(II) Complex

Schiff base ligand （HL） derived from 4-hexylaniline with isatin （1H-indole-2,3-dione） and its complexes with Cu（Ⅱ）, Ni（Ⅱ） were prepared and characterized by analytical, spectroscopic （IR, UV-Vis, Mass） techniques, electrical conductivity, magnetic and thermal measurements. The crystal and molecular structure of [Cu（HL）2Cl2] was determined by a single-crystal X-ray diffraction study. The molecular structure of the title compound has an inversion center on the Cu atom.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Subtraction of liposome signals in cryo-EM structural determination of protein-liposome complexes

Reconstituting membrane proteins in liposomes and determining their structure is a common method for determining membrane protein structures using single-particle cryo-electron microscopy(cryo-EM).However,the strong signal of liposomes under cryo-EM imaging conditions often interferes with the structural determination of the embedded membrane proteins.Here,we propose a liposome signal subtraction method based on single-particle two-dimensional(2D)classification average images,aimed at enhancing the reconstruction resolution of membrane proteins.We analyzed the signal distribution characteristics of liposomes and proteins within the 2D classification average images of protein–liposome complexes in the frequency domain.Based on this analysis,we designed a method to subtract the liposome signals from the original particle images.After the subtraction,the accuracy of single-particle three-dimensional(3D)alignment was improved,enhancing the resolution of the final 3D reconstruction.We demonstrated this method using a PIEZO1-proteoliposome dataset by improving the resolution of the PIEZO1 protein.

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.

Synergistic Optimization of Buried Interface by Multifunctional Organic-Inorganic Complexes for Highly Efficient Planar Perovskite Solar Cells

For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is challenging to effectively optimize this interface as it is buried beneath the perovskite film.Herein,we have designed and synthesized a series of multifunctional organic-inorganic(OI)complexes as buried interfacial material to promote electron extraction,as well as the crystal growth of the perovskite.The OI complex with BF4−group not only eliminates oxygen vacancies on the SnO_(2) surface but also balances energy level alignment between SnO_(2) and perovskite,providing a favorable environment for charge carrier extraction.Moreover,OI complex with amine(−NH_(2))functional group can regulate the crystallization of the perovskite film via interaction with PbI2,resulting in highly crystallized perovskite film with large grains and low defect density.Consequently,with rational molecular design,the PSCs with optimal OI complex buried interface layer which contains both BF4−and−NH_(2) functional groups yield a champion device efficiency of 23.69%.More importantly,the resulting unencapsulated device performs excellent ambient stability,maintaining over 90%of its initial efficiency after 2000 h storage,and excellent light stability of 91.5%remaining PCE in the maximum power point tracking measurement(under continuous 100 mW cm−2 light illumination in N2 atmosphere)after 500 h.

DNA-free genome editing in grapevine using CRISPR/Cas9 ribonucleoprotein complexes followed by protoplast regeneration

CRISPR/Cas9 genome editing technology can overcome many limitations of traditional breeding,offering enormous potential for crop improvement and food production.Although the direct delivery of Cas9-single guide RNA(sgRNA)ribonucleoprotein(RNP)complexes to grapevine(Vitis vinifera)protoplasts has been shown before,the regeneration of edited protoplasts into whole plants has not been reported.Here,we describe an efficient approach to obtain transgene-free edited grapevine plants by the transfection and subsequent regeneration of protoplasts isolated from embryogenic callus.As proof of concept,a single-copy green f luorescent protein reporter gene(GFP)in the grapevine cultivar Thompson Seedless was targeted and knocked out by the direct delivery of RNPs to protoplasts.CRISPR/Cas9 activity,guided by two independent sgRNAs,was confirmed by the loss of GFP f luorescence.The regeneration of GFP−protoplasts into whole plants was monitored throughout development,confirming that the edited grapevine plants were comparable in morphology and growth habit to wild-type controls.We report the first highly efficient protocol for DNA-free genome editing in grapevine by the direct delivery of preassembled Cas9-sgRNA RNP complexes into protoplasts,helping to address the regulatory concerns related to genetically modified plants.This technology could encourage the application of genome editing for the genetic improvement of grapevine and other woody crop plants.

Encapsulation of Ru(II) Polypyridine Complexes for Tumor-Targeted Anticancer Therapy

Ru(II)polypyridine complexes have attracted much attention as anticancer agents because of their unique photophysical,photochemical,and biological properties.Despite their promising therapeutic profile,the vast majority of compounds are associated with poor water solubility and poor cancer selectivity.Among the different strategies employed to overcome these pharmacological limitations,many research efforts have been devoted to the physical or covalent encapsulation of the Ru(II)polypyridine complexes into nanoparticles.This article highlights recent developments in the design,preparation,and physicochemical properties of Ru(II)polypyridine complex-loaded nanoparticles for their potential application in anticancer therapy.

Probing electronic structures of transition metal complexes using electron paramagnetic resonance spectroscopy

Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,how to extract the underlying electronicstructure information inevitably poses a major challenge to beginners,in particular for systems with S>1/2.In fact,the physical principles of transition metal EPR have long been well-established and since 1970s a series of dedicated voluminous monographs have been published already.Not surprisingly,they are not appropriate stating points for novices to grasp a panorama of the profound theory prior to scrutinizing in-depth references.The present review aims to fill this gap to provide a perspective of transition metal EPR and unveil some peculiar subtleties thereof on the basis of our recent work.

A Theoretical Study of Tris-(o-benzoquinonediimine)-First-Row Divalent Transition Metal Complexes

The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.

Pathfinder-Based Simulation and Optimization of Evacuation of Large Commercial Complexes

Large commercial complexes are large in scale, complex in function, and located in densely populated areas that are prone to casualties due to unfavorable evacuation. To comprehend the safety evacuation of large commercial complex buildings in China, investigate the safety evacuation problems encountered during the evacuation process and the evacuation optimization design strategy, the paper uses Pathfinder to build a simulation model based on literature research and study to simulate the evacuation of personnel in a large commercial complex in Dalian and explore its problems during the evacuation process. The results show that the type of personnel has an effect on the large commercial complex’s evacuation simulation results;the total number of evacuees is non-linearly correlated with the time change curve;some staircases take a long time to evacuate and have a low utilization rate. To improve evacuation efficiency, optimization suggestions for safety exits, evacuation stairs, and evacuation channels are made based on the results.

2,4-Dinitrophenyl Ether of Polyvinyl Alcohol and Polymer Bound Anionic SIGMA Complexes

A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.

Synthesis and Characterisation of Cr(III) and Co(II) Schiff Base Complexes

Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investigated by elemental analysis, molar conductance measurements, infrared spectroscopy, electronic spectroscopy, and 1HNMR spectroscopy. The elemental analysis data suggested a 1:1 [M:L] ratio for the complexes. The molar conductance measurements of the complexes indicate their electrolytic nature in DMSO as a solvent. The absorption bands in the electronic spectra verified an octahedral environment around the metal ions in the complexes.

全耳内镜下耳屏软骨-软骨膜复合体在上鼓室外侧壁重建中的临床应用

目的探究全耳内镜下耳屏软骨-软骨膜复合体在上鼓室外侧壁重建中的临床应用。方法选取2020年6月~2023年6月间徐州市中心医院收治的58例进行上鼓室外侧壁重建的胆脂瘤患者,根据采用修复材料的不同分为对照组及观察组各29例。对照组采用耳屏软骨膜进行上鼓室外侧壁重建,观察组采用耳屏软骨-软骨膜复合体进行上鼓室外侧壁重建,两组患者均于全耳内镜下进行手术。统计患者术中出血量、手术时间,术后3个月复查听力情况、干耳情况及耳道功能改善情况,术后随访6个月鼓膜愈合情况。结果与术前比较,术后3个月气导听阈、气骨导差降低(P<0.05),与对照组比较,观察组气导听阈、气骨导差降低(P<0.05);与对照组比较,观察组干耳率、耳道功能良好率、听力提高成功率均升高,干耳时间缩短,但耳屏愈合时间增加(P<0.05);与对照组比较,观察组手术时间缩短,术中出血量减少(P<0.05);观察组、对照组术后并发症总发生率分别为13.79%、24.14%,二者比较差异无统计学意义(P>0.05);观察组愈合良好率高于对照组(86.21%vs.62.07%)(P<0.05),两组患者耳膜穿孔(10.34%vs.24.14%)、鼓膜移位(3.45%vs.6.90%)及鼓膜回缩(0.00%vs.6.90%)发生情况比较,差异无统计学意义(P>0.05)。结论全耳内镜下耳屏软骨-软骨膜复合体在上鼓室外侧壁重建中有利于改善患者听力,有利于术后恢复。

东昆仑大格勒地区稀有和稀土矿化碱性杂岩体的发现及意义

稀有、稀土元素由于其特殊的属性对国民经济、国家安全和科技发展具有重要的战略意义。与碱性岩类相关的稀有、稀土矿产资源储量十分丰富,近年来对其勘探和开发越来越受到重视。青海省地质调查院在东昆仑中段大格勒地区首次发现了稀有和稀土矿化碱性杂岩体,岩石类型主要为含尖晶石磷灰石蛇纹石化橄榄岩、含磷灰石金云母霞石单斜辉石岩、橄榄辉长岩、含磷灰石金云母角闪石岩、磁铁矿化含橄榄石磷灰石碳酸岩等,其中含矿岩石为碳酸岩、橄榄岩、辉石岩等。矿石矿物主要为烧绿石、铌钽铁矿、磷灰石、独居石、钛铁矿。现初步圈定Nb、P矿体一条,矿体厚3.8~56.56 m,Nb_(2)O_(5)品位最高6.9%,平均0.71%;P_(2)O_(5)品位最高14.5%,平均品位5.6%,Ta和REE也伴有矿化,显示了很好的含矿性。这一发现大大拓展了青藏高原稀有、稀土矿的找矿空间,为发现新的、优质的稀有稀土矿产提供重要启示,具有重要的找矿和战略意义。

复杂结构内爆炸冲击波传播的大规模计算方法研究

为研究爆炸冲击波在矿井巷道等复杂地下密闭空间内的传播过程及衰减规律,提出了一种基于数据流的分块续算方法.该方法解决了计算资源的大量浪费问题,实现了大尺寸复杂地下密闭空间内冲击波传播的大规模、高效率、高精度数值模拟.方形坑道内爆过程的数值结果与实验结果基本一致,证明了该计算方法的准确性.标准模型算例全尺寸计算与分块续算数值模拟结果的误差在0.33%以内,且续算方法在给定算例下相比普通全尺寸计算节约了88.68%的计算核时,证明该方法不仅能保证计算过程的准确性,而且还极大地提高了计算效率.同时,对一个包含长方体型工房和圆柱形分叉泄压洞的大尺寸复杂结构内的爆炸问题进行了数值模拟,结果表明:冲击波超压在泄压洞内是以波动衰减的趋势逐渐减小的,且其衰减速度比在自由场的小;T型分流时管道间采用直角交汇或缩小管道直径在一定程度上有利于冲击波超压的衰减.数值模拟结果表明,基于数据流的分块续算方法可用于地下空间等大尺度复杂结构防爆抗爆设计的理论指导.

取代基位置对2,4-二苯基吡啶类铱磷光配合物光物理性能的影响

铱磷光配合物具有高的发光效率、良好的热稳定性和发光颜色容易调节等优势,在有机发光二极管(OLED)、电化学发光池(LEC)、光催化、肿瘤诊断和传感器等领域有着重要的应用前景,是综合性能最优的电致磷光配合物。其颜色调控主要通过改变主配体和辅助配体的化学结构来实现,如通过改变配体的共轭程度、在配体上引入具有不同供/吸电子能力的取代基、在不同位置引入相同的取代基等方式可以实现发光颜色的调节,其中取代基的位置对铱磷光配合物光物理性能影响的研究较少。研究甲基处于不同取代位置对铱磷光配合物光物理性能的影响,以甲基处于2位和4位或3位和5位的2,4-二苯基吡啶为主配体、2,2,6,6-四甲基庚二酮为辅助配体,合成出2个新的铱磷光配合物(2,4-2Me-dppy)_(2)Ir(tmd)和(3,5-2Me-dppy)_(2)Ir(tmd)。通过元素分析、核磁共振谱和单晶X射线衍射等测试了配合物的组成和空间结构,两个配合物均呈稍微扭曲的八面体构型,空间群分别为C 12/c 1和P-1,晶系分别为单斜和三斜;通过热重分析研究了配合物的热稳定性,两个配合物均具有较好的热稳定性,热分解温度分别为307和318℃;通过紫外可见光谱和光致发光光谱研究了配合物的光物理性能,两个配合物在溶液中发射波长分别为545和572 nm,溶液中量子产率分别为70%和92%。进一步探讨了取代基位置对铱磷光配合物光物理性能的影响,研究发现:甲基所处的位置对2,4-二苯基吡啶类铱磷光配合物的发光颜色和发射波长有着显著的影响。与甲基处于2位和4位得到的铱磷光配合物相比,甲基处于3位和5位时得到的铱配合物的发射波长产生了明显的红移,为纯正的黄光发射,是一种潜在的黄光材料,并有望在OLED照明中得到应用。

核心素养导向的学科实践:内在逻辑与学习进程

学科实践是核心素养导向下的学科学习新形态,指向学生应对复杂问题情境的胜任力与协作交往的道德力的培育。学科实践包含人类实践、专业实践和个体实践,其紧紧围绕着学科知识与学科实践、学科观念与学科实践的互通关系而展开,知识在人类实践中产生又在指导和规约实践中得以发展,个体观念则在经历学科知识生产和发展的思维过程和实践过程中得以建构,再应用于实际问题解决以发展学生的学科理解力与学科实践力。学科实践以感性实践为起点,在复杂问题解决学习中通过理性实践与协作探究深化知识理解,并在知行循环中实现知识迁移与知识应用。让学科实践在学校教育中得以真正落实,需明确“学用合一”的学习理念,以“学科心理”来融通系列学习活动,厘清进阶性学科问题与问题链的现实路径,并致力构建意义协商的学习共同体。

复杂背景下基于YOLOv7-tiny的图像目标检测算法

“黑飞”无人机一旦带有炸弹等物品,会对人们带来威胁。对在公园、游乐场、学校等复杂背景下“黑飞”的无人机进行目标检测是十分必要的。前沿算法YOLOv7-tiny属于轻量级网络,具有更小的网络结构和参数,更适合检测小目标,但在识别小目标无人机时出现特征提取能力弱、回归损失大、检测精度低的问题;针对此问题,提出了一种基于YOLOv7-tiny改进的无人机图像目标检测算法YOLOv7-drone。首先,建立无人机图像数据集;其次,设计一种新的注意力机制模块SMSE嵌入到特征提取网络中,增强对复杂背景下无人机目标的关注度;然后,在主干网络中融入RFB结构,扩大特征层的感受野,丰富特征信息以增强特征提取的鲁棒性;然后,改进网络中的特征融合机制,通过新增小目标检测层,增加对小尺度目标的检测精度;然后,改变损失函数提高模型的收敛速度,减少损失以增强模型的鲁棒性;最后,引入可变形卷积(Deformable convolution, DCN),更好的根据目标本身形状进行特征提取,提升了检测精度。在PASCAL VOC公共数据集上进行对比实验,结果表明改进后的算法YOLO7-drone相比于YOLOv7-tiny,平均精度(map@0.5)提升了6%;在自制无人机数据集上进行实验,结果表明YOLOv7-drone与原算法相比,平均精度(map@0.5)提高了6.1%,并且检测速度为72帧/s;与YOLOv5l、YOLOv7目标检测算法进行对比实验,结果表明改进后的算法在平均精度(map@0.5)上分别高于对比算法4%、3.1%,验证了文中算法的可行性。