全文获取类型
收费全文 | 8633篇 |
免费 | 1154篇 |
国内免费 | 1064篇 |
专业分类
化学 | 4991篇 |
晶体学 | 102篇 |
力学 | 408篇 |
综合类 | 88篇 |
数学 | 685篇 |
物理学 | 2312篇 |
无线电 | 2265篇 |
出版年
2024年 | 30篇 |
2023年 | 139篇 |
2022年 | 223篇 |
2021年 | 250篇 |
2020年 | 273篇 |
2019年 | 302篇 |
2018年 | 210篇 |
2017年 | 232篇 |
2016年 | 376篇 |
2015年 | 421篇 |
2014年 | 472篇 |
2013年 | 666篇 |
2012年 | 676篇 |
2011年 | 643篇 |
2010年 | 599篇 |
2009年 | 517篇 |
2008年 | 630篇 |
2007年 | 516篇 |
2006年 | 516篇 |
2005年 | 487篇 |
2004年 | 374篇 |
2003年 | 344篇 |
2002年 | 285篇 |
2001年 | 261篇 |
2000年 | 212篇 |
1999年 | 181篇 |
1998年 | 165篇 |
1997年 | 123篇 |
1996年 | 118篇 |
1995年 | 102篇 |
1994年 | 80篇 |
1993年 | 69篇 |
1992年 | 63篇 |
1991年 | 58篇 |
1990年 | 42篇 |
1989年 | 31篇 |
1988年 | 22篇 |
1987年 | 20篇 |
1986年 | 25篇 |
1985年 | 17篇 |
1984年 | 13篇 |
1983年 | 8篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1974年 | 5篇 |
1964年 | 2篇 |
1963年 | 2篇 |
1935年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
利用密度泛函理论方法研究了作为空穴迁移载体的蛋白质复合的DNA三聚体(Protonated arginine…guanine…cytosine, ArgH+-GC)的氢键性质. 结果表明, 空穴迁移通过该载体单元时此类氢键表现为亚稳态, 且具有明显的负离解能. 正常情况下ArgH+基团在大小沟均能与GC碱对形成氢键, 且具有正的离解能. 然而, 当空穴转移至此将削弱氢键至亚稳态, 使之具有一定的离解势垒和负的离解能. 这种势垒抑制的负离解能现象意味着由于空穴俘获导致此三聚体结构单元在它的ArgH+…N7/O6键区储存了一定的能量(约108.78 kJ/mol). 该氢键离解通道受控于此键区两个相关组分之间的静电排斥和氢键吸引之间的平衡以及这两个相反作用随氢键距离不同的衰减速率. 基于电子密度分布的拓扑性质以及键临界点的Laplacian数值分析澄清了此类特殊的能量现象主要源自通过高能氢键(ArgH+…N7/O6)连接的授受体间的静电排斥. 进一步空穴俘获诱导的G→C质子转移可扩展负离解能区至ArgH+…N7/O6和Watson-Crick(WC) 氢键区. 另外, ArgH+ 结合到GC的大小沟增加其电离势, 因此削弱其空穴传导能力, 削弱程度取决于ArgH+与GC的距离. 推而广之, 在protonated lysine-GC和protonated histidine-GC体系也可观察到类似的现象. 显然, 此类性质可调的亚稳态氢键可调控DNA空穴迁移机理. 此工作为理解蛋白质调控的DNA空穴迁移机理提供了重要的能量学信息. 相似文献
992.
论述了教学研究的重要性和复杂性。提出撰写教学研究论文应符合先进性、创新性、实证性、示范性和发展性等原则。介绍了教学研究涉及的主要领域,研究的主要内容和方法,对如何开展各领域教学研究并撰写高水平的教学研究论文进行了讨论并给出了示例。 相似文献
993.
Rajangam Vinodh Mani Ganesh Mei Mei Peng Aziz Abidov Muthiahpillai Palanichamy Wang Seog Cha Hyun-Tae Jang 《高分子科学》2015,33(2):224-235
Microporous hypercross-linked conjugated quinonoid chromophores represent a novel class of amorphous polymers, synthesized by the reaction of anthracene with dimethoxy methane in the presence of FeCl3 catalyst. Their N2 adsorption isotherms confirm their microporous nature. Diffuse reflectance UV-Visible(DRS UV-Vis) spectroscopy confirms their matrix built with the conjugated quinonoids by their broad light absorption characteristics extending from 1000 nm to 200 nm with the absorbance maximum close to 400 nm. The catalyst cross-linked anthracene with ―CH2― bridges and subsequently dehydrogenating them to form quinonoids. Their Fourier transform infrared(FTIR) spectra showed their characteristic quinonoid vibrations between 1600 and 1700 cm-1. The synthesis of polymers was carried out at 30, 40, 50, 60, 70 and 80 ℃, but the quinonoid content of the polymer obtained at 80 ℃ was higher than that of the others. Their scanning electron microscopy(SEM) images showed microspheres of 1 to 5 μm size built with tiny particles. Their surfaces were not smooth. The polymer synthesized at 80 ℃ showed 5.1 wt% CO2 sorption at 25 ℃ and 0.1 MPa, but when it was recross-linked, the CO2 sorption increased to 8 wt%. Hence, hypercross-linked conjugated quinonoid chromophores of anthracene are good for sorption of CO2. 相似文献
994.
以Sm3+作为激活剂,Bi3+作为辅助激活剂,采用水热法合成Ca1-x-ySmxBiySi O3前驱体,然后在1 100℃焙烧得到系列橙红色荧光粉。用X-射线衍射仪、扫描电镜和荧光分光光度计和傅里叶变换红外光谱等手段对样品的组成、结构和形貌及其发光性质进行分析和表征。分析结果表明:产物都为三斜晶系结构的Ca1-x-ySmxBiySi O3和四方结构的方石英Si O2共熔体。在405 nm近紫外光激发下,产物的发射光谱由3个峰组成,发射峰值位于566、606和650 nm处,分别归属于Sm3+的4G5/2→6HJ/2(J=5,7,9)跃迁。产物的激发光谱在405 nm有很强的发射带,与近紫外LED芯片匹配。随着Sm3+掺量的增加,样品发光强度先增强后减弱,当Sm3+的物质的量分数为3%时发光强度达到最大,浓度猝灭机理为电偶极-电偶极相互作用。当Bi3+的物质的量分数在0.3%~1.5%时,对产物Ca0.97Sm0.03Si O3的荧光强度起敏化作用。Sm3+和Bi3+的最佳物质的量分数分别为3%和0.5%。 相似文献
995.
Jing‐Mei Bao Min‐Hong Jiang Shu‐Ling Lin Zhi‐You Su Gui‐Hua Tang Sheng Yin 《Helvetica chimica acta》2015,98(10):1387-1394
Five new cassane diterpenoids, caesalmins I–M ( 1 – 5 ), and 23 known analogs were isolated from the seeds of Caesalpinia minax. Their structures were elucidated by spectroscopic methods and comparison with reported data. The antioxidant properties of 1 – 28 were determined by the method of oxygen radical absorbance capacity of fluorescein (ORAC‐FL), and 14 compounds exhibited good antioxidant activities with ORAC‐FL values of 2.24–4.89 Trolox equivalents. The structure? activity relationship of the active compounds was also discussed. 相似文献
996.
Characterization of Novel Aminobenzylcantharidinimides and Related Imides by Proton NMR Spectra and Their Effects on NO Induction 下载免费PDF全文
Ing‐Jy Tseng Pen‐Yuan Lin Shiow‐Yunn Sheu Wan‐Ni Tung Ching‐Tung Lin Mei‐Hsiang Lin 《中国化学会会志》2015,62(1):59-63
Various acidic anhydrides including cantharidin were converted into corresponding aminobenzylcantharidinimide 3a and analogous imides 3b~k (at the ortho, meta, and para positions) with 35%~87% yields by reacting with aminobenzylamines and triethylamine. The two methyl side chains of cantharidinimides 3ao , 3am , and 3ap, and related imides had more than two chiral centers; the lone pair of electrons of nitrogen displayed a different chemical shift and coupling constant in H‐NMR spectra when the amino group of benzylamine was in the ortho position. These cantharidinimides had parent aniline, pyridine, and naphthalene plane structures, and the primary amine nucleophilicity and basicity might reflect the inductive electron’s negative effect on chemical shifts. We prepared cantharidinimides by heating the reactants cantharidin 1a , aliphatic and aromatic acid anhydrides, primary benzylic amines, and aniline derivatives to ca. 200 °C with 3 mL of dry toluene, and 1~2 mL of triethylamine in high‐pressure sealed tubes (Buchi glasuster 0032) to produce cantharidinimides and their analogues in good yields. The para‐aminobenzylic imides showed greater inhibition of nitric oxide (NO) synthesis by NO synthase (NOS) than did ortho‐ and meta‐aminobenzylic imides. Compound 3fp , para‐aminobenzylic norbonane‐imide, had the most potent effect on inducible NOS among the tested compounds and showed 35% inhibition. 相似文献
997.
Fabrication of the Monolithic Fiber for the Solid Phase Micro‐extraction of Malachite Green 下载免费PDF全文
A monolithic fiber of molecularly imprinted polymer (MIP) was prepared by in situ polymerization within the capillary with an inner diameter of 530 µm. It was carried out in 8 min by microwave irradiation using malachite green (MG) as a template molecule, α‐methacrylic acid (MAA) as a functional monomer, acetonitrile (ACN) as a porogenic solvent, ethylene dimethacrylate (EDMA) as a crosslinker, azodiiso‐butyronitrile (AIBN) as a thermal initiator. The resulted MIP fibers were pushed out from the capillary, eluted and inserted in the capillary again, which successfully used for the solid phase microextraction (SPME) procedure. The factors affecting the extraction of MG, such as the molar ratio of template/monomer (MG/MAA), concentration of NaCl, extraction and desorption time, and extraction and desorption solvents were investigated in detail. The selectivity of the MIP fibers was compared using MG analogues crystal violet (CV) and non‐analogue Sudan II. It was also employed for the pretreatment of trace MG in the fish feed followed by high‐performance liquid chromatography (HPLC) detection. Under the optimal conditions, the linear range of MG was 10‐600 μg/L, the detection limit (LOD) was 1.23 μg/L and the recovery of spiked fish feed sample was 88.7~113.9%. 相似文献
998.
999.
The cloud point extraction (CPE) preconcentration of ultra-trace amount of mercury species prior to reverse-phase high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) detection was studied. Mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were transformed into hydrophobic chelates by reaction with sodium diethyldithiocarbamate, and the hydrophobic chelates were extracted into a surfactant-rich phase of Triton X-114 upon heating in a water bath at 40 °C. Ethylmercury was found partially decomposed during the CPE process, and was not included in the developed method. Various experimental conditions affecting the CPE preconcentration, HPLC separation, and ICP-MS determination were optimized. Under the optimized conditions, detection limits of 13, 8 and 6 ng l−1 (as Hg) were achieved for MeHg+, PhHg+ and Hg2+, respectively. Seven determinations of a standard solution containing the three mercury species each at 0.5 ng ml−1 level produced relative standard deviations of 5.3, 2.3 and 4.4% for MeHg+, PhHg+ and Hg2+, respectively. The developed method was successfully applied for the determination of the three mercury species in environmental water samples and biological samples of human hair and ocean fish. 相似文献
1000.
A visual test paper by taking common filter paper as solid support for extremely strong concentrated acidity has been developed in this contribution with a new synthesized isoindole compound starting from p-phenylenediamine and the coupled fluorogenic reagent of o-phthaldialdehyde-β-mercaptoethanol. It was very easy for semiquantitative detection of acidity in the range of 0.2-18 M ([H+]) in extreme acidic solution based on the color changes of the solution or the visual test paper prepared by immerging filter paper slides into the solution of the new synthesized reagent. Quantitative detection of concentrated strong acids could be successfully constructed through the linear relationship exists between the absorbance of the chromogenic reagent at 510 nm and the acid concentrations. 相似文献