全文获取类型
收费全文 | 1608篇 |
免费 | 133篇 |
国内免费 | 402篇 |
专业分类
化学 | 1473篇 |
晶体学 | 10篇 |
力学 | 205篇 |
综合类 | 35篇 |
数学 | 137篇 |
物理学 | 283篇 |
出版年
2024年 | 3篇 |
2023年 | 20篇 |
2022年 | 55篇 |
2021年 | 86篇 |
2020年 | 96篇 |
2019年 | 57篇 |
2018年 | 52篇 |
2017年 | 77篇 |
2016年 | 81篇 |
2015年 | 58篇 |
2014年 | 83篇 |
2013年 | 154篇 |
2012年 | 106篇 |
2011年 | 98篇 |
2010年 | 75篇 |
2009年 | 111篇 |
2008年 | 104篇 |
2007年 | 129篇 |
2006年 | 99篇 |
2005年 | 84篇 |
2004年 | 73篇 |
2003年 | 61篇 |
2002年 | 49篇 |
2001年 | 41篇 |
2000年 | 43篇 |
1999年 | 24篇 |
1998年 | 31篇 |
1997年 | 24篇 |
1996年 | 20篇 |
1995年 | 27篇 |
1994年 | 26篇 |
1993年 | 14篇 |
1992年 | 16篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有2143条查询结果,搜索用时 500 毫秒
91.
以功能化氮配体为导向,以4,7-二苯基-1,10-菲咯啉为原料,经季铵化、氧化、卤化和醚化合成了一类新型的2,9-二烷氧基-4,7-二苯基-1,10-菲咯啉配体5a~5e。再以Xantphos为膦配体,通过原位配位方法合成一系列氮磷杂配铜光敏剂(CuPS A~H),在均相光解水制氢体系中研究其光敏活性。制氢结果表明,以2,9-二乙氧基为较佳取代基,CuPS D的催化产氢总转换数(TON)可达270。在光电物理性能分析中,发现这类杂配铜配合物都有一个相似的氧化还原电位(Eoxd=-0.8 V,Ered=-1.2 V)。具有乙氧取代基的铜配合物CuPS D相对于其他取代基的铜基配合物,荧光最弱,表明乙氧基有助于提高荧光淬灭效率,增强铜光敏剂的光化学转换能力。 相似文献
92.
Hui Tang Can-Hui Zheng Xiao-Hui Ren Jia Liu Na Liu Jia-Guo Lv Ju Zhu You-Jun Zhou 《中国化学快报》2013,24(3):219-222
A series of 1-(benzylamino)-2-(2,4-difluorophenyl)-3-(1H-1,2,4-triazol-l-yl)propan-2-ols compounds were synthesized and evaluated for their antifungal activities in vitro.The results showed that compounds 6A and 6B exhibited good antifungal activity.Compound 6A8 showed the strongest antifungal activity,which was significantly higher than that of the lead compounds and positive-control drugs Fluconazole and Itraconazole.In particular,the antifungal activity of compound 6A8 against Candida albicans and Candida krusei(MIC80 both at 0.00097μg/mL) was 515 and 64 times that of Fluconazole,respectively.The structure-activity relationships of the synthesized compounds were discussed,and the docking model of the target compounds with fungal lanosterol 14α-demethylase (CYP51) was analyzed. 相似文献
93.
Květa Kalíková Petr Kozlík Martin Gilar Eva Tesařová 《Journal of separation science》2013,36(15):2421-2429
Hydrophilic interaction liquid chromatography is a separation technique suitable for the separation of moderately and highly polar compounds. Various stationary phases (SPs) for hydrophilic interaction liquid chromatography are commercially available. While the SPs based on the same type of ligand are available from different providers, they can display a distinct retention characteristics and separation selectivity. The current work is focused on characterization and comparison of the separation systems of two amide‐based HPLC columns from two producers, i.e. XBridge Amide column and TSK gel Amide‐80 column. Several characterization procedures (tests) were used to investigate the differences between these columns. The chromatographic behavior of selected analytes indicates that multimodal interactions are responsible for retention and separation on these columns. Multiple testing approaches were used in order to reveal subtle differences between the SPs. Both amide‐based columns showed certain differences in retention, selectivity, and plate counts. Based on the tests used in this study, we conclude that the investigated columns provide a different degree of H‐bonding interactions. 相似文献
94.
95.
96.
Sie-Tiong Ha Teck-Ming Koh Hong-Cheu Lin Guan-Yeow Yeap Yip-Foo Win Siew-Teng Ong 《Liquid crystals》2013,40(9):917-925
Two homologous series of 2-(4-alkanoyloxybenzylidenamino)benzothiazoles and 2-(2-hydroxy-4-alkanoyloxybenzylidenamino)benzothiazoles were synthesised and characterised. Their molecular structures differed wherein the latter comprised a lateral hydroxyl group, unlike the former. Spectroscopic techniques such as FT-IR, 1H & 13C NMR and mass spectrometry together with elemental analysis were employed to elucidate the molecular structures. The transition temperatures and their mesophases were determined by differential scanning calorimetry, optical polarising microscopy and X-ray diffraction techniques. Members with decanoyloxy till hexadecanoloxy chain in the series without the lateral hydroxyl group each exhibited a smectic A phase, while those in the series with the lateral hydroxyl group were non-mesogenic. The mesomorphic properties of the present series were compared with other structurally related series to establish the chemical structure–mesomorphic properties relationship. 相似文献
97.
Jie Han Feng‐Yan Zhang Zhi Chen Juan‐Yu Wang Li‐Rong Zhu Mei‐Li Pang 《Liquid crystals》2013,40(12):1359-1365
A series of new compounds based on aromatically 2,5‐disubstituted 1,3,4‐oxadiazoles without flexible chains, formulated as p‐R–C6H4–(OC2N2)–(p‐C6H4)2–R′ with (i) R = CH3O, R′ = CH3O, CH3S, F, H (Ia–Id), (ii) R = CH3S, R′ = CH3O, CH3S, F, H (IIa–IId) and (iii) R = F, R′ = CH3O, CH3S, F, H (IIIa–IIId) (p‐C6H4 and OC2N2 represent a p‐phenylene spacer and a 1,3,4‐oxadiazole ring, respectively), were synthesised and characterised by 1H and 13C NMR, MS and HRMS techniques. Mesomorphic properties were investigated using differential scanning calorimetry and polarizing optical microscopy. All of the target compounds (except Id, IId, IIIc and IIId) exhibited an enantiotropic nematic mesophase with high melting temperatures. The liquid crystalline properties of these compounds were influenced greatly by polarity, steric factors and positions of the terminal groups. The effect of the terminal groups on the liquid crystal properties is discussed. 相似文献
98.
表面活性剂的临界胶束浓度(CMC)是个非常重要的物质特性参数, CMC在研究表面活性剂的工业应用和生物利用方面发挥着关键作用. 本工作提出了一个新的拓扑指数—扩展距离矩阵, 建立了一个稳定的构效关系模型, 并对175种表面活性剂的临界胶束浓度进行了计算预测. 结果表明, 基于新的拓扑指数建立的构效关系模型计算临界胶束浓度能给出稳定可靠的预测结果, 其预测结果相关性系数R2(training set)=0.9295, 相对标准偏差ARD(training set)=8.20%, R2(testing set)=0.9257, ARD(testing set)=6.76%. 与文献中模型预测结果的对比表明, 本工作在稳定性和可靠性上均有显著改善. 相似文献
99.
20世纪60年代,美国密执安州立大学Rosenberg发现了顺铂具有抗癌活性,开辟了金属类抗肿瘤药物研究的新领域.经过40余年的研究,已相继成功开发了卡铂、奈达铂、奥沙利铂、舒铂、洛铂和双环铂等铂类抗肿瘤药物.虽然对于铂类抗肿瘤药物研究取得了一定的成绩,但在临床使用过程中也存在一些问题,如其毒副作用和抗药性,限制了其在临床上的进一步广泛应用.为了解决这些问题,科研工作者开始寻找新的金属类抗肿瘤药物以弥补现有铂类抗肿瘤药物的不足.在金属元素中,唯有钯(II)与铂(II)配合物具有相似或相同的结构特征,进而表现出相近或相似的化学性质.因此,继铂类抗肿瘤配合物后,钯(II)配合物作为潜在抗肿瘤药物成为一个诱人的领域.本文综述了近年来钯(II)类抗肿瘤药物的研究进展,并探讨了其构效关系,这对于指导新型钯(II)类抗肿瘤药物的合成具有重要的参考价值. 相似文献
100.
Dibenzyl trisulfide (DTS) is a natural compound with potential cancer-preventive properties occurring in Petiveria alliacea L., an ethnomedicinal plant native to the Americas. Previous studies revealed its inhibitory activity toward cytochrome P450 (CYP)1 enzymes, key in the activation of environmental pollutants. Accordingly, the aim of this study was to design novel DTS analogues, aimed at improving not only inhibitory activity, but also specificity toward CYP1A1. This was achieved by targeting interactions with CYP1A1 residues of identified importance. Three-dimensional structures for the novel analogues were subjected to molecular docking with several CYP isoforms, before being ranked in terms of binding affinity to CYP1A1. With three hydrogen bond donors, two hydrogen bond acceptors, a molecular mass of 361 Da, and a log P of 3.72, the most promising DTS analogue obeys Lipinski's rule of five. Following synthesis and in vitro validation of its CYP1A1-inhibitory properties, this compound may be useful in future cancer-preventive approaches. 相似文献