全文获取类型
收费全文 | 1247篇 |
免费 | 91篇 |
国内免费 | 58篇 |
专业分类
化学 | 1315篇 |
晶体学 | 6篇 |
综合类 | 2篇 |
数学 | 3篇 |
物理学 | 70篇 |
出版年
2024年 | 3篇 |
2023年 | 24篇 |
2022年 | 46篇 |
2021年 | 78篇 |
2020年 | 62篇 |
2019年 | 43篇 |
2018年 | 50篇 |
2017年 | 49篇 |
2016年 | 76篇 |
2015年 | 54篇 |
2014年 | 60篇 |
2013年 | 88篇 |
2012年 | 67篇 |
2011年 | 78篇 |
2010年 | 65篇 |
2009年 | 65篇 |
2008年 | 58篇 |
2007年 | 58篇 |
2006年 | 47篇 |
2005年 | 49篇 |
2004年 | 46篇 |
2003年 | 27篇 |
2002年 | 28篇 |
2001年 | 14篇 |
2000年 | 17篇 |
1999年 | 19篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 9篇 |
1995年 | 9篇 |
1994年 | 10篇 |
1993年 | 13篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有1396条查询结果,搜索用时 31 毫秒
81.
A simple, rapid, and highly sensitive method for simultaneous analysis of anti‐inflammatory drugs (naproxen, ibuprofen, and mefenamic acid) in diluted human serum was developed using the electrochemically controlled solid‐phase microextraction coupled to ion mobility spectrometry. A conducting molecularly imprinted polymer film based on polypyrrole was synthesized for the selective uptake and release of drugs. The film was prepared by incorporation of a template molecule (naproxen) during the electropolymerization of pyrrole onto a platinum electrode using cyclic voltammetry method. The measured ion mobility spectrometry intensity was related to the concentration of analytes taken up into the films. The calibration graphs (naproxen, ibuprofen, and mefenamic acid) were linear in the range of 0.1–30 ng/mL and detection limits were 0.07–0.37 ng/mL and relative standard deviation was lower than 6%. On the basis of the results obtained in this work, the conducting molecularly imprinted polymer films as absorbent have been applied in the electrochemically controlled solid‐phase microextraction and ion mobility spectrometry system for the selective clean‐up and quantification of trace amounts of anti‐inflammatory drugs in human serum samples. Scanning electron microscopy has confirmed the nano‐structure morphology of the polypyrrole film. 相似文献
82.
Sazlinda Kamaruzaman Peter C. Hauser Mohd Marsin Sanagi Wan Aini Wan Ibrahim Salasiah Endud Hong Heng See 《Analytica chimica acta》2013
A simple adsorption/desorption procedure using a mixed matrix membrane (MMM) as extraction medium is demonstrated as a new miniaturized sample pretreatment and preconcentration technique. Reversed-phase particles namely polymeric bonded octadecyl (C18) was incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a C18-MMM. Non-steroidal anti-inflammatory drugs (NSAIDs) namely diclofenac, mefenamic acid and ibuprofen present in the environmental water samples were selected as targeted model analytes. The extraction setup is simple by dipping a small piece of C18-MMM (7 mm × 7 mm) in a stirred 10 mL sample solution for analyte adsorption process. The entrapped analyte within the membrane was then desorbed into 100 μL of methanol by ultrasonication prior to high performance liquid chromatography (HPLC) analysis. Each membrane was discarded after single use to avoid any analyte carry-over effect. Several important parameters, such as effect of sample pH, salting-out effect, sample volume, extraction time, desorption solvent and desorption time were comprehensively optimized. The C18-MMM demonstrated high affinity for NSAIDs spiked in tap and river water with relative recoveries ranging from 92 to 100% and good reproducibility with relative standard deviations between 1.1 and 5.5% (n = 9). The overall results obtained were found comparable against conventional solid phase extraction (SPE) using cartridge packed with identical C18 adsorbent. 相似文献
83.
Novel 1,2,4‐triazole isonucleosides (1 and 2) were efficiently synthesized starting from D‐ribose and D‐xylose, respectively. The key steps were condensation of cyclic sulfate 8 with methyl‐1,2,4‐triazole‐3‐carboxylate and nucleophilic displacement of the tosylate 15 with methyl‐1,2,4‐triazole‐3‐carboxylate, respectively. 相似文献
84.
Dopamine, rotigotin, ladostigil, and rasagiline analogues 2-amino-4,5,6-trimethoxyindane and 1-amino-5,6,7-trimethoxyindane were synthesized starting from 5,6,7-trimethoxyindan-1-one for the first time with 34% and 45% total yields. α-Carboxylation of indanone, reduction of ketone group with Et3SiH, basic hydrolysis of ester, Curtius reaction of the acid, and addition of BnOH afforded the corresponding carbamate. Pd-C-catalyzed hydrogenolysis of carbamate and deprotonation of amine hydrochloride with NaOH gave the dopamine and rotigotin analogue 2-aminoindane. Reduction of 5,6,7-trimethoxyindan-1-one with NaBH4 afforded the alcohol, which was then converted to the azide derivative via Mitsunobu reaction with diphenylphosphoryl azide; Pd-C catalyzed hydrogenation of the azide to the amine hydrochloride and then deprotonation of the amine hydrochloride with NaOH furnished the ladostigil and rasagiline analogue 1-aminoindane. These amines and BnOH were reacted with CSI to produce sulfamoyl carbamates, which were converted to sulfamides via Pd-C-catalyzed hydrogenolysis reaction with 20% and 25% total yields. 相似文献
85.
A method for the synthesis of sultam thioureas via a different 1,4,2-dithiazolidine 1,1-dioxide ring-forming reaction is presented here. The syntheses of nine sultam thioureas were achieved in 53–81% yield by reacting N-substituted chloromethanesulfonamides with thiocarbamoyl isothiocyanates, which were formed in situ from the reaction of 5-(disubstituted amino)-3H-1,2,4-dithiazole-3-thiones with triphenylphosphine. Importantly, this method successfully allowed the substituent of the ring nitrogen atom to be varied. Additionally, the structures of four sultam thioureas were confirmed by x-ray diffraction. 相似文献
86.
A Beckmann Rearrangement/Friedel-Crafts strategy was utilized to prepare 5-amidotetralones in high yield. 相似文献
87.
Dr. Pablo Trigo‐Mouriño Dr. M. Carmen de la Fuente Dr. Roberto R. Gil Dr. Víctor M. Sánchez‐Pedregal Dr. Armando Navarro‐Vázquez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14989-14997
The conformational state of 8‐chloro‐1‐methyl‐2,3,4,5‐tetrahydro‐1H‐3‐benzazepine hydrochloride (lorcaserin) in water has been determined on the basis of one‐bond and long‐range C? H residual dipolar coupling (RDC) data along with DFT computations and 3JHH coupling‐constant analysis. According to this analysis, lorcaserin exists as a conformational equilibrium of two crown‐chair forms, of which the preferred conformation has the methyl group in an equatorial orientation. 相似文献
88.
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
89.
人体端粒由富含鸟嘌呤(G)的DNA重复序列组成,该序列在一定的条件下可以形成G-四链体DNA的结构.小分子化合物诱导该结构的形成并使之稳定,不但可以抑制端粒酶的活性或降低癌基因的转录表达而达到抗肿瘤的目的,还可以作为G-四链体DNA的探针,辅助G-四链体DNA生物功能的研究及与之相关疾病的诊断.因此,G-四链体DNA稳定剂的设计是近年来化学生物学的重要前沿领域之一.到目前为止,G-四链体DNA稳定剂主要可分为有机小分子化合物和金属配合物.本文重点综述这两方面特别是后者的最新研究进展. 相似文献
90.
随着人口老龄化进程的发展,阿尔茨海默症(AD)已成为威胁中国和世界人口健康和经济的重大疾病.本文综述了近年来AD病理的分子机制的新进展,分析了其中金属代谢的意义.研究发现,在AD进程中,围绕淀粉样斑块(AP)和神经缠绕斑(NFT)的形成,多因素相互联系并发挥作用,这些主要因素包括金属内稳态、胰岛素抵抗、神经炎症、线粒体和血脑屏障改变等.与AD病理过程密切相关的主要蛋白质均参与了金属元素的生理代谢过程,而细胞金属离子的内稳态失衡加剧了AD病理的恶化.金属药物在AD诊断和治疗中可能具有以下的发展潜力:(1)AD早期诊断探针;(2)调节金属内稳态的配体和/或微量元素补充;(3)抗糖尿病金属配合物;(4)神经元和血脑屏障(BBB)保护金属药物. 相似文献