Polymer Solar Cells Based on the Copolymers of Naphtho[1,2-c：5,6-c]bis（1,2,5-thiadiazole） and Alkoxylphenyl Substituted Benzodithiophene with High Open-Circuit Voltages

Two novel naphtho[1,2-c：5,6-c]bis（1,2,5-thiadiazole） and alkoxylphenyl substituted benzodithiophene based copolymers were developed as the donor materials for polymer solar cells. The resulting copolymers exhibit broad absorption bands in the range of 500--800 nm in thin films and deep highest occupied molecular orbital energy levels of-5.39 eV and -5.36 eV, respectively. The best device performance was achieved by PI, with an open-circuit voltage of 0.85 V, a short-circuit current density of 8.65 mA·cm^-2, a fill factor of 37.8%, and a power conversion efficiency of 2.78%.

Synthesis and antitumor activity of N^1-acetylamino-(5-alkyl/aryl-1,3,4-thiadiazole-2-yl)-5-fluorouracil derivatives

A new series of N^1-acetylamino-（5-alkyl/aryl- 1,3,4-thiadiazole-2-yl）-5-fluorouracil derivatives were designed and synthesized. These compounds have not been reported in literature, and their structure chemical were confirmed by IR, ^1H NMR and MS （HRMS）. The results of antitumor inhibitory activity test showed that some compounds possess more potent antitumor inhibitory activity than 5-fluorouracil.

Microwave Assistant Synthesis and Dimeric Crystal Structure of 2-(((6-Chloropyridin-3-yl)-methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole

The title compound 2-(((6-chloropyridin-3-yl)methyl)thio)-5-(pyridin-4-yl)-1,3,4-thiadiazole 5(C26H18Cl2N8S4) was synthesized, and its structure was confirmed by 1H NMR, MS and elemental analyses and X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 9.452(4), b = 12.335(4), c = 13.017(5) A, α = 90.624(5), β = 110.541(5), γ =104.879(4)°, Dc = 1.561 g/cm3, Z = 2, V = 1364.9(9) A3, F(000) = 656, the final R = 0.0300 and w R = 0.0635 for 4206 observed reflections with I 】 2σ(I). The preliminary biological test showed that the title compound has activities against Stemphylium lycopersici(Enjoji) Yamamoto, Fusarium oxysporum. sp. cucumebrium, and Botrytis cinerea with inhibitory activities to be 9.82%, 44.44% and 20.00%, respectively.

Synthesis and evaluation of in vitro antibacterial activity of novel 2,5-disubstituted-l,3,4-thiadiazoles from fatty acids

A series of new 1-（alkenoyl/hydroxyalkenoyl）-4-benzoyl-thiosemicarbazides 2a-d and 2-benzamide-5-alkenyl/hydroxyalk- enyl-1,3,4-thiadiazoles 3a-d were synthesized from fatty acid hydrazides. Structure of all these compounds was confirmed by IR, IH NMR, Sac NMR, mass spectra and elemental analysis. The bioassay results indicate that some compounds 2e, 2d, 3e and 3d have good antibacterial activity.

Synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with potential bioactivity in PEG-400

An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The key advantages of this protocol are the shorter reaction time,higher yields,lower cost,simple workup,and environment-friendly compared to conventional organic solvent reaction.The present method does not involve any hazardous organic solvent or catalyst.

白藜芦醇激活细胞外信号调节激酶5信号蛋白促进小鼠MC3T3-E1细胞增殖

背景:细胞外信号调节激酶5信号蛋白对生物体的存活不可或缺,白藜芦醇能通过多种途径促进成骨细胞增殖,但其是否能通过细胞外信号调节激酶5信号蛋白调控成骨细胞功能还需进一步验证。目的:探究细胞外信号调节激酶5对MC3T3-E1细胞增殖以及相关分泌蛋白的调控作用,进一步验证白藜芦醇通过激活细胞外信号调节激酶5完成上述过程。方法:小鼠MC3T3-E1前成骨细胞分别用完全培养基、XMD8-92(细胞外信号调节激酶5抑制剂)、表皮生长因子(细胞外信号调节激酶5激活剂)和白藜芦醇单独干预及XMD8-92+表皮生长因子、白藜芦醇+XMD8-92干预后,通过Western blot检测各组细胞内细胞外信号调节激酶5、磷酸化细胞外信号调节激酶5蛋白,增殖相关蛋白Cyclin D1、CDK4、PCNA,以及成骨细胞分泌蛋白骨保护素、核因子κB受体活化因子配体的表达情况,使用细胞免疫荧光染色检测各组细胞外信号调节激酶5、骨保护素和核因子κB受体活化因子配体荧光强度,使用EdU染色检测各组细胞增殖情况。白藜芦醇干预MC3T3-E1细胞的适宜浓度及时间由细胞形态学观察和CCK-8实验确定。结果与结论:①细胞外信号调节激酶5信号蛋白的激活能有效促进MC3T3-E1细胞增殖、上调骨保护素/核因子κB受体活化因子配体比值;②白藜芦醇干预MC3T3-E1细胞的适宜浓度及时间为5μmol/L,24 h;③白藜芦醇可以激活细胞外信号调节激酶5信号蛋白,进而促进成骨细胞增殖,并上调骨保护素/核因子κB受体活化因子配体比值;④研究结果表明,白藜芦醇可以通过激活细胞外信号调节激酶5信号蛋白促进MC3T3-E1细胞增殖,并通过激活细胞外信号调节激酶5信号蛋白上调骨保护素/核因子κB受体活化因子配体比值。

Synthesis,Crystal Structure and Biological Activity of N-tert-butyl-N-(4-methyl-1,2,3-thiadiazole)-5-yl-N’-(4-methyl-1,2,3-thiadiazole)-5-formyl-N’-3,5-dichloropyridin-2-yl-diacylhydrazine

The title compound N-tert-butyl-N-（4-methyl-1,2,3-thiadiazole）-5-yl-N＇-（4-me-thyl-1,2,3-thiadiazole）-5-formyl-N＇-3,5-dichloropyrid-2-yl-diacylhydrazines （C18H17Cl2N7O3S2, Mr = 514.41） has been synthesized by the reaction of N-tert-butyl-N＇-3,6-dichloropyridine-2-formyl hydrazine with 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride and triethylamine, and its structure was characterized by 1H NMR, HR MS, and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group C2/c with a = 27.726（8）, b = 11.045（3）, c = 14.507（4）A, β = 96.758（4）°, Z = 8, V = 4412（2） A^3, Dc = 1.549 g/cm^3, μ = 0.521 mm^-1, F（000） = 2112, R = 0.0405 and wR = 0.1153. X-ray analysis indicates that all rings are non-planar in this molecule. The bioassay results indicate that both the title compound and the positive control RH-5992 have weak fungicide activities, while the title compound has good insecticidal activity against Plutella xylostella L. and no insecticidal activity against Culex pipiens pallens.

Synthesis,Crystal Structure,and Biological Activity of Naphthalen-2-yl4-methyl-1,2,3-thiadiazole-5-carboxylate

The title compound naphthalen-2-yl-4-methyl-1,2,3-thiadiazole-5-carboxylate （C 14 H 10 N 2 O 2 S,M r=270.31） was synthesized by the reaction of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride with 2-naphthol,and its structure was characterized by IR,1 H NMR,high-resolution mass spectrometry and single-crystal X-ray diffraction.The crystal belongs to orthorhombic,space group Pbcn with a=23.475（5）,b=9.6640（19）,c=10.814（2）,β=90.00°,Z=8,V=2453.2（9） 3,M r=270.30,D c=1.464 g/cm 3,μ=0.262 mm-1,F（000）=1120,R=0.0444 and wR=0.1099.X-ray analysis revealed that the thiadiazole and naphthalene rings were non-planar,while the thiadiazole ring and the ester group were essentially planar,and two intermolecular hydrogen bonds C（6） H（6）···O（1） and C（14） H（14）···O（1） were observed.The preliminary biological test showed that the title compound had antifungal and antivirus activities against tobacco mosaic virus.

Synthesis,Crystal Structure,DFT Studies and Antifungal Activity of 5-(4-Cyclopropyl-5-((3-fluorobenzyl)sulfonyl)-4H-1,2,4-triazol-3-yl)-4-methyl-1,2,3-thiadiazole

5-（4-Cyclopropyl-5-（（3-fluorobenzyl）sulfonyl）-4H-1,2,4-triazol-3-yl）-4-methyl-1,2,3-thiadiazole was synthesized and recrystallized from Et OH. The compound was characterized by ^1H NMR,MS,elemental analysis and X-ray diffraction. The structure-active relationship and the antifungal activity based on density functional theory calculation（DFT） and antifungal activities were investigated. The compound crystallizes in the monoclinic space group P121/n1 with a = 8.929（3）,b=12.715（4）,c=15.161（5） A°,β = 106.142（3）o,V = 1653.3（9） A°3,Z = 4 and R = 0.0393 for 3930 observed reflections with I 〉 2σ（I）. Theoretical calculation of the title compound was carried out with B3LYP/6-31G（d,p）. The full geometry optimization was carried out using the 6-31G（d,p） basis set.The frontier orbital energy and atomic net charges were discussed. The observed results of the compound have been compared with theoretical results and the experimental data show good agreement with the calculated values. The compound exhibits good antifungal activity.

One-pot synthesis of 2,5-disubstituted-1,3,4-thiadiazoles under ultrasonic irradiation

A facile one-pot synthesis of 2,5-disubstituted-1,3,4-thiadiazoles was achieved by ultrasonic irradiation of a mixture of 1-naphthylacetyl chloride, NH4CNS, CH2Cl2 and PEG-400 for 1.5 h at 10–20 °C and subsequent irradiation for 1.5 h in the presence of N-arylglycine hydrazides. This method requires short time and gives thiadiazoles in high yields.

A novel series of 2,5-disubstituted 1,3,4-thiadiazoles as potential anticonvulsant agent

In pursuit for better antiepileptic drug and the importance of semicarbazones and 2,5-disubstituted 1,3,4-thiadiazoles as anticonvulsant pharmacophore, a series of novel N-（{5-[（6-methyl-l-benzofuran-3-yl）methyl]-l,3,4-thiadiazol-2-yl}carba- mothioyl）-2/3/4-substitutedbenzamide were designed, synthesized and evaluated for their anticonvulsant activity. The findings of the present studies confirmed that the pharmacophore model with four binding sites is crucial for anticonvulsant activity. Structure-activity relationships among synthesized compounds were also established.

Synthesis, Crystal Structure and Biological Activity of N-(tert-butyl)-N'-(2-(4-chlorophenyl)acetyl)-5-methyl-1,2,3-thiadiazole-4-carbohydrazide

The title compound N-（tert-butyl）-N＇-（2-（4-chlorophenyl）acetyl）-5-methyl-1,2,3-thiadiazole-4-carbohydrazide （C16H19ClN4NaO2S, Mr = 366.86） has been synthesized, and its structure was characterized by IR, 1H NMR, H RMS and single-crystal X-ray diffraction. The crystal of the title compound belongs to triclinic, space group Pī with a = 8.464（2）, b = 10.192（2）, c = 11.757（2）, α = 68.48（3）, β = 76.31（3）, γ = 80.86（3）°, Z = 2, V = 2024.6（10） 3, Dc = 1.333 g/cm3, μ = 0.339 mm-1, F（000） = 384, R = 0.0450 and wR （Ⅰ 〉 2σ（Ⅰ）） = 0.1234. X-ray analysis indicates one N-H…N intermolecular hydrogen bond and no π-π stacking interactions are observed in this crystal structure. The preliminary biological test shows that the title compound has fungicidal activity and antivirus activities against tobacco mosaic virus.

Syntheses and Crystal Structures of Two Novel Cobalt(Ⅱ) Complexes with 2-Amino-5-substituted-1,3,4-thiadiazole as Ligands

Two novel cobalt（Ⅱ） compounds were obtained and characterized by X-ray sing- le-crystal diffraction, IR, 1H NMR and elemental analysis. Compound 1 crystallizes in monoclinic, space group P21/n, with a = 18.046（4）, b = 11.335（3）, c = 19.157（5）A, β = 92.707（3）°, Z = 4, V = 3914.4（16） A3, Mr = 968.56, Dc = 1.644 g/cm3, μ = 1.378 mm^-1, F（000） = 1960, the final R = 0.0367 and wR = 0.0895. The crystal of compound 2 is of monoclinic, space group P211c with a = 8.7253（10）, b = 10.9031（13）, c = 18.235（2）A,β = 93.2210（10）°, Z = 4, V = 1732.0（3）A3, Mr = 464.21, Dc = 1.780 g/cm3,μ = 1.560 mm-1, F（000） = 932, the final R = 0.0322 and wR = 0.0743.

2,5-Dimercapto-1,3,4-Thiadiazole(DMCT)-Based Polymers for Rechargeable Metal-Sulfur Batteries

Organosulfur materials are a sustainable alternative to the present-day layered oxide cathodes in lithium-based batteries.One such organosulfur material that was intensely explored from the 1990s to early 2010s is 2,5-dimercapto-1,3,4-thiadiazole(DMCT).However,research interest declined as the electrode reactions with DMCT were assumed to be too sluggish to be practical.Armed with the advances in metal-sulfur batteries,we revisit DMCT-based materials in the form of poly[tetrathio-2,5-(1,3,4-thiadiazole)],referred to as pDMCT-S.With an appropriate choice of electrode design and electrolyte,pDMCT-S cathode paired with a Li-metal anode shows a capacity of 715 mA h g^(-1)and a Coulombic efficiency of 97.7%at a C/10 rate,thus quelling the concerns of sluggish reactions.Surprisingly,pDMCT-S shows significantly improved long-term cyclability compared to a sulfur cathode.Investigations into the origin of the stability reveals that the discharge product Li-DMCT in its mesomeric form can strongly bind to polysulfides,preventing their dissolution into the electrolyte and shuttling.This unique mechanism solves a critical problem faced by sulfur cathodes.Encouragingly,this mechanism results in a stable performance of pDMCT-S with Na-metal cells as well.This study opens the potential for exploring other organic materials that have inherent polysulfide sequestering capabilities,enabling long-life metal-sulfur batteries.

Synthesis, Characterization and Crystal Structure of a Dinuclear Silver(I) Complex: [AgL(NO_3)]_2 (L= 2-Acetamido-5-methyl-1,3,4-thiadiazole)

The title complex [AgL（NO3）]2 1, where L = 2-acetamido-5-methyl-1,3,4-thiadiazole, was prepared from the reaction of 2-acetamido-5-methyl-1,3,4-thiadiazole with AgNO3 at room temperature and its structure has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P2t/c with a = 12.5454（8）, b = 11.9672（12）, c = 6.8925（6） A, β = 98.468（2）°. V= 1023.51（15） A^3, Mr= 3127.08, Dc = 2.123 g/cm^3, Z= 4, μ（MoKoσ） = 2.174 mm^-1, F（000） = 640, R = 0.0259 and wR = 0.0580 for 1787 observed reflections with I 〉 2σ（I）. Complex 1 self-assembls into a quasi-three-dimensional network consisting of adjacent dimers through intermolecular Ag...O weak interactions.

One-dimensional Zigzag Chain Composed of HgI_2 Unit and 2,5-Bis(4-pyridyl)-1,3,4-thiadiazole:[HgI_2(C_(12)H_8N_4S)]

The title compound, [HgI2（C12H8N4S）], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086（2）, b = 6.0365（6）, c = 20.286（2）°A,β= 108.818（5）°, V = 1632.7（3）°A^3, Mr = 694.67, Z = 4, D, = 2.826 g/cm^3,μ= 13.331 mm^-1, F（000） = 1240, S = 1.108, the final R = 0.0438 and wR = 0.0934 for 3085 observed reflections （I〉 2σ（I））. The Hg（Ⅱ） atom is coordinated by two 2,5-bis（4-pyridyl）-1,3,4-thiadiazole （L） molecules and two iodine anions in a distorted tetrahedral coordination geometry. Mercury atoms are linked by the organic ligands to form a one-dimensional zigzag chain. It is noteworthy that such 1D zigzag chains are extended into a two-dimensional double layer framework through I…I interactions

基于改进YOLOv5的红花目标检测算法研究

为实现农业非结构环境下采摘机器人对红花的准确识别,提出了一种基于改进YOLOv5的红花目标检测算法。将CBAM注意力机制嵌入到YOLOv5网络,提高了小尺寸目标物在高层次特征中的表现力;建立一种Alpha-IoU目标位置损失函数对原损失函数GIOU存在的梯度消失问题进行改进,提高了被遮挡红花的预测率,并通过在目标检测网络中增加分割检测模块,提高宽和高小于最低像素的小目标物检测精度,利用图像扩增数据集对改进后的YOLOv5算法进行训练,再分别与改进前后YOLOv5网络和Faster R-CNN网络在不同红花品种、不同自然光照情况、不同天气条件和不同遮挡情况下进行对比。试验结果表明:改进后的YOLOv5算法P值、R值分别为90.45%和0.90,对非结构环境下盛开期的未采摘红花mAP值达到94.48%,在不同影响因素下都可以准确识别出红花且置信度较高,可为红花采摘机器人自动化作业中的红花识别提供技术支持。

过表达溶质载体家族1成员5和敲低慢病毒载体构建及稳定转染RAW264.7细胞株

背景:溶质载体家族1成员5(solute carrier family 1 member 5,SLC1A5)在多种疾病中发挥了潜在作用,但确切作用机制尚不清楚。构建稳定的SLC1A5过表达和敲低细胞模型可为深入研究SLC1A5在疾病中的确切作用机制以及发现潜在治疗靶点提供有力的实验工具。目的:构建小鼠SLC1A5过表达和敲低的慢病毒载体,以建立稳定转染的RAW264.7细胞株,为深入探讨SLC1A5在炎症中的作用提供实验基础。方法:根据SLC1A5基因序列设计合成引物并使用聚合酶链反应扩增该基因片段。将目的基因定向接入经Age I/Nhe I酶切的载体质粒GV492中构建重组慢病毒质粒,对阳性克隆进一步筛选后测序比对结果;pHelper1.0质粒载体、pHelper2.0质粒载体、目的质粒载体与293T细胞共同培养并转染,获得慢病毒原液进行包装和滴度测定;在此基础上,通过体外培养RAW264.7细胞,确定嘌呤霉素工作质量浓度;不同滴度的慢病毒分别与RAW264.7细胞共同培养,根据荧光强度确定转染效率;用嘌呤霉素挑选出稳定转染细胞,实时荧光定量聚合酶链反应和蛋白免疫印迹方法检测稳定转染细胞株的SLC1A5基因和蛋白表达水平。结果与结论:(1)测序序列与目的序列一致提示重组慢病毒载体构建成功;(2)过表达SLC1A5慢病毒的滴度为1×10~9 TU/mL,敲低SLC1A5慢病毒的滴度为3×10~9 TU/mL;(3)确定RAW264.7细胞嘌呤霉素工作质量浓度为3μg/mL;(4)过表达/敲低SLC1A5慢病毒转染RAW264.7细胞的最佳条件皆为HiTransG P转染增强液且感染复数值等于50;(5)过表达SLC1A5稳转细胞株中SLC1A5基因和蛋白的表达量明显上调,而敲低SLC1A5稳转细胞株中SLC1A5基因和蛋白的表达量显著下调。结果表明,成功构建了小鼠SLC1A5过表达和敲低的慢病毒载体并获得稳定转染的RAW264.7细胞株。

5-羟甲基糠醛在CuPd(111)上的加氢反应机理研究

采用密度泛函理论,利用包含零点能校正的PBE-D3方法研究了5-羟甲基糠醛在双金属催化剂CuPd(111)上表面的加氢还原反应,考虑了两种反应路径,第一种反应路径是侧链上的醛基氧首先发生加氢反应生成F-CHOH中间体,然后F-CHOH中间体继续加氢生成2,5-二羟甲基呋喃;第二种反应路径是侧链上的醛基碳先加氢原还原生成F-CH_(2)O中间体,生成的F-CH_(2)O进一步加氢还原生成2,5-二羟甲基呋喃.计算了两种竞争反应路径的活化能垒和反应热,结果表明,5-羟甲基糠醛在CuPd(111)面加氢还原生成2,5-二羟甲基呋喃的最佳反应路径为:F-CHO→F-CHOH→F-CH_(2)OH.

Synthesis, X-ray Structure and Bioactivity of N-4-Methyl-1,2,3-thiadiazole-5-carbonyl-N′-3,5- dichloro-4-(1,1,2,2-tetrafluoroethoxyl)phenyl Urea

The title compound N-4-methyl-1,2,3-thiadiazole-5-carbonyl-N＇-3,5-dichloro-4- （1,1,2,2- tetrafluoroethoxyl）phenyl urea （C13H8Cl2F4N4O3S, Mr = 447.19） has been synthesized from 4-methyl- 1,2,3-thiadiazole-5-carbonyl chloride as the starting material, and its structure was characterized by proton Nuclear Magnetic Resonance （1H NMR）, Infra Red Spectroscopy （IR）, high-resolution mass spectroscopy （HRMS）, and single-crystal X-ray diffraction. The crystal of the title compound belongs to triclinic, space group Pi with a = 6.0780（8）, b = 11.3760（14）, c = 12.1440（18） A, α = 96.887（7）, β = 91.027（12）, γ= 104.252（13）°, Z = 2, V= 806.98（19）A3, Dc = 1.840 g/cm3, μ= 0.601 mm-1, F（000） = 448, R = 0.0450 and wR = 0.0869. X-ray analysis indicates that the 1,2,3-thiadiazole ring is not coplanar with the phenyl ring, and the dihedral angle is 33.57°. Two intermolecular hydrogen bonds N（2）-H…O（1 ）, S（1 ）…H-C（11）, and three weak intermolecular interactions, C（11）…O（1）, N（1）…O（2） and S…O（1）, are observed. The bioassay results indicate that the title compound has good insecticidal activity against Culex pipiens pallens and good induction activity for tobacco against tobacco mosaic virus which is equal to that of TDL.