全文获取类型
收费全文 | 29155篇 |
免费 | 5046篇 |
国内免费 | 4102篇 |
专业分类
化学 | 22466篇 |
晶体学 | 380篇 |
力学 | 1435篇 |
综合类 | 322篇 |
数学 | 3089篇 |
物理学 | 10611篇 |
出版年
2024年 | 35篇 |
2023年 | 554篇 |
2022年 | 640篇 |
2021年 | 904篇 |
2020年 | 1193篇 |
2019年 | 1211篇 |
2018年 | 1064篇 |
2017年 | 969篇 |
2016年 | 1439篇 |
2015年 | 1501篇 |
2014年 | 1763篇 |
2013年 | 2287篇 |
2012年 | 2618篇 |
2011年 | 2804篇 |
2010年 | 2022篇 |
2009年 | 1887篇 |
2008年 | 2088篇 |
2007年 | 1878篇 |
2006年 | 1752篇 |
2005年 | 1547篇 |
2004年 | 1188篇 |
2003年 | 1015篇 |
2002年 | 1023篇 |
2001年 | 744篇 |
2000年 | 703篇 |
1999年 | 560篇 |
1998年 | 411篇 |
1997年 | 365篇 |
1996年 | 334篇 |
1995年 | 273篇 |
1994年 | 298篇 |
1993年 | 223篇 |
1992年 | 191篇 |
1991年 | 143篇 |
1990年 | 131篇 |
1989年 | 119篇 |
1988年 | 67篇 |
1987年 | 57篇 |
1986年 | 57篇 |
1985年 | 48篇 |
1984年 | 30篇 |
1983年 | 20篇 |
1982年 | 20篇 |
1981年 | 13篇 |
1980年 | 21篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1974年 | 10篇 |
1973年 | 11篇 |
1957年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 515 毫秒
991.
O/W微乳液中聚吡咯超微粒子的制备 总被引:4,自引:0,他引:4
选择合适的SDBS/吡咯/H2O三组分O/W微乳液与吡咯单体共存的两相体系,以单体相为单体源,在O/W三组分微乳液中进行了吡咯聚合,所得聚吡咯粒子大小仅为2~3nm,分布较均匀,且具有较好的导电性能. 相似文献
992.
Zachary M. Schulte Yeon Hye Kwon Yi Han Chong Liu Lin Li Yahui Yang Austin Gamble Jarvi Sunil Saxena Gtz Veser J. Karl Johnson Nathaniel L. Rosi 《Chemical science》2020,11(47):12807
Metal–organic frameworks constructed from multiple (≥3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn–Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H2/CO2 separation ability of bMOF-200. We examine the H2/CO2 separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H2/CO2 separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H2 and CO2 and a significantly improved H2/CO2 separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H2/CO2 separations.Tailorable multicomponent MOFs and MOF membranes for efficient H2/CO2 separation. 相似文献
993.
纳米尺寸团簇NinZrn(n=3~5)的几何结构与成键规律研究 总被引:3,自引:0,他引:3
根据化学键理论与拓扑原理,设计了团簇NinZrn(n=3-5)的可能几何构型,并用从头算方法进行构型优化,结果表明,由NiZr组成的团簇原子间的Zr-Zr和Zr-Ni键明显较强,而Ni-Ni的成键较弱,并发与NinZrn(n=3-5)团簇电子性质与有机烯烃分子等瓣相似,原子之间的成键按照强弱相间的规则分布。 相似文献
994.
Microdialysis sampling coupled with liquid chromatography-electrochemical detection (LC-ED) was developed and applied to determine the interaction of thiopurine (TP) with bovine serum albumin (BSA). A nickel hexacyanoferrate (NiHCNFe) modified electrode was fabricated and used as the working electrode in LC-ED for the determination of TP. Cyclic voltammetric experiments demonstrate that this chemically modified electrode (CME) can effectively catalyze the electrooxidation of TP. The mechanism of the catalytic oxidation of TP at the CME involves an 'EC' process. In the LC-ED, the CME also shows good stability and reproducibility for the determination of TP. The limit of detection is 5.0 x 10(-7) mol l(-1) for 6-TP with a signal-to-noise ratio of 3. The utility of microdialysis as a quantitative sampling technique for in vitro studies of drug-protein interactions was studied. The microdialysis experiments were performed in phosphate buffer solution (pH 7.4) containing different molar ratios of the drug and protein at 37 degrees C. The collected microdialysis sample with unbound TP was analyzed at the NiHCNFe CME in the LC-ED. The relative recovery of TP determined in vitro is 18.3% at a perfusion rate of 1.0 microl min(-1) and the RSD is about 2.1%. The association constant and the number of binding sites on a BSA molecule calculated with the Scatchard equation are 3.72 x 10(-3) (1 mol(-1)) and 1.51, respectively. This method provides a fast, sensitive and simple technique for the study of drug-protein interactions. 相似文献
995.
在密度泛函理论的框架下, 采用嵌入点电荷簇模型研究了O2在MgO(001)完整和缺陷表面上的吸附.用电荷自洽的方法确定了点电荷的值.计算结果表明, O2倾向吸附在低配位的角Mg2+端.并且发现, 当O2为平躺吸附时,键长有较大的拉伸,将有利于O2的解离.同时,分别计算了使用裸簇和嵌入表观±2.0 e点电荷簇模型时的吸附能,并与采用电荷自洽方法的计算值进行了比较.结果表明,电荷自洽方法更能有效反映簇周围的环境,得到的计算结果能够较好地与实验值吻合.最后,分别计算了不同吸附情况下O2的振动频率. 相似文献
996.
Surface plasmon resonances of silver triangle nanoplates: graphic assignments of resonance modes and linear fittings of resonance peaks 总被引:3,自引:0,他引:3
The extinction spectra of five silver equilateral triangle plates with a fixed thickness of 10 nm and side lengths of 50, 100, 150, 200 ,and 250 nm, respectively, have been simulated by the discrete dipole approximation (DDA) method in which a geometric object of interest is meshed and represented by a lattice of spatial dipoles. Irradiated by an incident plane wave with a given propagation direction and polarization state, each triangle nanoplate presents three surface plasmon resonance (SPR) peaks in the range of 300 to 1200 nm. At a given peak, every complex spatial oscillatory vector derived by DDA (corresponding to a certain dipole in the meshed target) is orthogonally resolved into three basic oscillations. Each basic component can be subsequently expressed by two parameters, amplitude (P) and phase angle (varphi). The distributions of six such physical parameters of all the dipoles in the selected cross plane of the target are illustrated colorfully in plots as a graphic characterization and assignment of the SPR modes. The graphic method is applied to reveal the local fine features of SPR modes. And it provides direct evidence for classifying SPR peaks which belong to different triangle nanoplates and appear at different wavelengths. Three SPR modes are recognized graphically and the wavelengths of SPR peaks are found to have linear relationships with the side lengths of the triangle nanoplates. 相似文献
997.
Si-Geun Lee Young-Whan Park Dae-Woo Nam Hyosun Lee Kwang Ho Song 《Journal of organometallic chemistry》2004,689(16):2586-2592
Methylene-bridged ansa-metallocene complexes bearing substituents on the cyclopentadienyl (Cp) and fluorenyl (Flu) moieties, namely methylene[9-(2,7-di-tert-butyl)fluorenyl(2-(1,3-dimethylcyclopentadienyl))]zirconium dichloride (1a) and its analogue, methylene[(9-(2,7-di-tert-butyl)fluorenyl(2-(1-methyl-3-phenyl)cyclopentadienyl))]zirconium dichloride (2a), have been prepared from (2,7-di-tert-butyl)-9-prop-2-ynyl-9H-fluorene (2). This procedure includes the use of 3-bromo-1-propyne which affords the methylene bridging unit by way of an intermolecular Pauson-Khand reaction in which norbornadiene and a pendant alkyne cyclize to form a ring that later becomes a substituted cyclopentadienyl group. Ethylene-norbornene (E-N) copolymerization was then carried out using these new complexes (1a and 1b) in the presence of methylaluminoxane (MAO) as a cocatalyst; these activities can be compared to that of isopropylene[9-fluorenyl-cyclopentadienyl]zirconium dichloride (3a). The activity of catalyst 1a was comparable to that of 3a but much higher than that of 2a. In addition, 1a shows higher norbornene insertion performance, and gives an E-N copolymer with a higher glass transition temperature (Tg) than 2a under identical conditions; both 1a and 2a give a lower Tg polymer than 3a does. 相似文献
998.
An intumescent flame retardant coating was prepared with resin, solvent and flame retardant system composed of ammonium polyphosphate-APP, pentaerythritol-PER and melamine-MEL. The modifiers such as molybdenum disilicide (MoSi2) and expandable graphite (EG) were used to improve the performances of the APP-PER-MEL coating. The effects of EG, MoSi2 and MoSi2/EG on the fireproofing time and char formation of the coating were investigated by using heat insulation test, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electric microscope (SEM). The results showed that by adding modifiers, the fireproofing time was prolonged and char formation rate was evidently enhanced. The largest improvement was achieved with 9 wt.% MoSi2/5 wt.% EG, XPS analysis indicated that the performance of anti-oxidation of the coating was improved by adding EG and MoSi2, and SEM images showed that a good synergistic effect was obtained through a ceramic-like layer produced by MoSi2 covered on the surface of “open-cellular” structural char. 相似文献
999.
The paramagnetic complexes formed in Friedel‐Crafts alkylation reaction systems are invistigated by electron spin resonance (ESR) spectroscopy, in room temperature ionic liquids system 1‐butyl‐3‐methyl‐limidazolium chloride‐aluminium chloride ([bmim]Cl‐AlCl3). The results indicate that ESR spectra observed are due to polycyclic aromatic radical cations formed from their parent hydrocarbons. ESR spectrum of spin adduct is obtained in an ionic liquid system composed of [bmim]Cl‐AlCl3. In acidic solution the 14N hyperfine coupling constant of 4‐oxo‐TEMPO, 2.15 mT, is appreciably larger due to an adduct formed with AlCl3. 相似文献
1000.