全文获取类型
收费全文 | 29721篇 |
免费 | 6021篇 |
国内免费 | 6492篇 |
专业分类
化学 | 21694篇 |
晶体学 | 660篇 |
力学 | 1943篇 |
综合类 | 735篇 |
数学 | 3959篇 |
物理学 | 13243篇 |
出版年
2024年 | 72篇 |
2023年 | 465篇 |
2022年 | 1047篇 |
2021年 | 1048篇 |
2020年 | 1187篇 |
2019年 | 1170篇 |
2018年 | 1055篇 |
2017年 | 1159篇 |
2016年 | 1292篇 |
2015年 | 1539篇 |
2014年 | 1841篇 |
2013年 | 2309篇 |
2012年 | 2612篇 |
2011年 | 2724篇 |
2010年 | 2218篇 |
2009年 | 2233篇 |
2008年 | 2477篇 |
2007年 | 2193篇 |
2006年 | 2088篇 |
2005年 | 1654篇 |
2004年 | 1407篇 |
2003年 | 1105篇 |
2002年 | 1093篇 |
2001年 | 1035篇 |
2000年 | 942篇 |
1999年 | 679篇 |
1998年 | 461篇 |
1997年 | 442篇 |
1996年 | 392篇 |
1995年 | 309篇 |
1994年 | 319篇 |
1993年 | 273篇 |
1992年 | 200篇 |
1991年 | 188篇 |
1990年 | 175篇 |
1989年 | 133篇 |
1988年 | 119篇 |
1987年 | 122篇 |
1986年 | 85篇 |
1985年 | 64篇 |
1984年 | 52篇 |
1983年 | 52篇 |
1982年 | 46篇 |
1981年 | 33篇 |
1980年 | 31篇 |
1979年 | 25篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 11篇 |
1959年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 417 毫秒
991.
A quantitative analysis method for penicillins including ampicillin (AmP), benzyl penicillin (BP), oxacillin (OA) and amoxycillin (AmO) is proposed that makes use of the totally internally reflected resonance light scattering (TIR-RLS) signal from the penicillin at the H2O/CCl4 interface in the presence of cetyltrimethylammonium bromide (CTMAB), and enables the pharmacokinetics of penicillin taken orally and excreted through urine to be monitored. Penicillin is coadsorbed with CTMAB at the H2O/CCl4 interface in neutral solution, resulting in the formation of ion associates that display greatly enhanced TIR-RLS signals (maximum at 368–372 nm). This enhanced TIR-RLS intensity was found to be proportional to the penicillin concentration over the range 0.2×10–6 to 2.2×10–6 mol L–1, with limits of determination (3) of 5.0×10–8 to 7.0×10–8 mol L–1. Pharmacokinetics studies performed using the present method show that the excretion of orally-taken ampicillin through urine has a half-time of 1.05 h and an excremental quantum over 8 h of 49.3%, respectively. 相似文献
992.
Nematic-isotropic interfaces exhibit novel dynamics due to anchoring of the liquid crystal molecules on the interface. The objective of this study is to demonstrate the consequences of such dynamics in the flow field created by an elongated nematic drop retracting in an isotropic matrix. This is accomplished by two-dimensional flow simulations using a diffuse-interface model. By exploring the coupling among bulk liquid crystal orientation, surface anchoring and the flow field, we show that the anchoring energy plays a fundamental role in the interfacial dynamics of nematic liquids. In particular, it gives rise to a dynamic interfacial tension that depends on the bulk orientation. Tangential gradient of the interfacial tension drives a Marangoni flow near the nematic-isotropic interface. Besides, the anchoring energy produces an additional normal force on the interface that, together with the interfacial tension, determines the movement of the interface. Consequently, a nematic drop with planar anchoring retracts more slowly than a Newtonian drop, while one with homeotropic anchoring retracts faster than a Newtonian drop. The numerical results are consistent with prior theories for interfacial rheology and experimental observations. 相似文献
993.
An organic-inorganic compound [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O4o(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O,2,2'-bipyridine (2,2'-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9)(A), β=96.992(3)°, V= 8365.0(6) (A)3, Dc= 3.214 g/cm3, Z = 4,μ(MoKα) = 17.269 mm-1 and F(000) = 7324.Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR =0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2'-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2'-bpy)2]2 cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2'-bpy)2}2 groups through bridging oxygen atoms. 相似文献
994.
Single crystals of a neutral, microporous, laminated metal-organic framework (MOF)[Fe(pydc)(4,4'-bipy)]xH(2)O (1xH(2)O)(H(2)pydc = 2,5-dicarboxypyridine, 4,4'-bipy = 4,4'-bipyridine) were generated by hydrothermal synthesis, and its crystal structure was determined. 1xH(2)O retains the framework robustness to ca. 370 degrees C and is insoluble in common organic solvents. By soaking in MeOH and EtOH solutions, 1xH(2)O was transformed directly from the parent single crystals into single crystals of 1xMeOH or 1xEtOH, respectively. Meanwhile, 1xH(2)O shrank to the guest-free framework (h) or (v), respectively, under appropriate heating (up to 160 degrees C in N(2)) or vacuum treatment (10 mmHg) at room temperature. Compared to that of 1xH(2)O, the unit-cell volume of 1xEtOH slightly increases by 2.9%, whereas those of (h) or (v) are reduced by 8.2 and 6.6%, respectively. The anhydrous (v) was found to be highly chemically reactive, taking up ethanol vapor to furnish the solvated crystal structure of an 'expanded' framework 1xEtOH. In a mixture of ethanol-DMF or ethanol-benzene, a selective exchange process was observed, with only ethanol molecules exchanged into the structure due to the limited free size of the channels in the framework of. All the transformed crystals have also been characterized by X-ray single-crystal diffraction to understand the crystal-to-crystal transformation, which have different free volumes (6.5-20.4%). 相似文献
995.
The effects of the hyperbranched polyester with hydroxyl end groups (HBPE‐OH) on the curing behavior and toughening performance of a commercial epoxy resin (diglycidyl ether of bisphenol A, DGEBA) were presented. The addition of HBPE‐OH into DGEBA strongly increased its curing rate and conversion of epoxide group due to the catalytic effect of hydroxyl groups in HBPE‐OH and the low viscosity of the blend at curing temperature. The improvements on impact strength and critical stress intensity factor (or fracture toughness, K1c) were observed with adding HBPE‐OH. The impact strength was 8.04 kJ m?1 when HBPE‐OH reached 15 wt% and the K1c value was approximately two times the value of pure epoxy resin when HBPE‐OH content was 20 wt%. The morphology of the blends was also investigated, which indicated that HBPE‐OH particles, as a second phase in the epoxy matrix, combined with each other as the concentration of HBPE‐OH increased. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
996.
HZSM-5分子筛焙烧脱铝的27Al MQMAS NMR研究 总被引:1,自引:0,他引:1
用29Si、27Al魔角旋转固体核磁共振(MAS NMR)结合二维多量子魔角旋转(2D MQMAS)技术对焙烧脱铝的HZSM-5分子筛中铝的配位状态进行了研究.结果表明,HZSM-5分子筛经焙烧后,在化学位移(δ)45处出现一宽峰信号,其主要来自扭曲四配位铝.通过二维三量子铝谱计算出扭曲四配位铝的四极作用常数约为5.2 MHz.对700和750 ℃焙烧样品的铝谱进行分峰拟合,发现在δ 30处又出现一个小峰,归属为非骨架五配位铝.同时,在750 ℃焙烧样品的二维多量子铝谱中直接观察到非骨架五配位铝的信号.焙烧温度低于700 ℃,脱铝不明显;高于700 ℃,引起分子筛骨架的显著脱铝.焙烧还造成部分骨架铝的信号变得“不可观测”. 相似文献
997.
Wang Li Cai Jiwen Mao Zon-Wang Feng Xiao-Long Huang Jin-Wang 《Transition Metal Chemistry》2004,29(4):411-418
Four novel dinickel complexes, coordinated by mixed ligands of tren and racemic amino acids, namely [Ni2(tren)2(dl-alaninato)(H2O)]I3·2H2O (1), [Ni2(tren)2(dl-leucinato)(H2O)]I3·2.5H2O (2), [Ni2(tren)2(dl-phenylalaninato)(H2O)]I3·H2O (3), and {[Ni2(tren)2(dl-histinato)](ClO4)3·1.5H2O}
n
(4), have been synthesized and structurally characterized by X-ray crystallography, FTIR, u.v. and e.s. spectra. They represent the first series of dinickel(II) complexes bridged by the unusual (N,O,O)-coordinated -amino acids. In complexes (1–3), one of the nickel(II) centers is coordinated by four N-atoms of the tren ligand, one O-atom of the carboxylate group of the amino acidato ligand and one H2O molecule. The other nickel(II) center is also coordinated by the four N-atoms of the tren ligand, one carboxylic O-atom and the amino N-atom of the amino acidato ligand, resulting in an asymmetric dinuclear core with chromophores of NiN4O2 and NiN5O. In the polymeric {[Ni2(tren)2(dl-histinato)](ClO4)3·1.5H2O}
n
(4), the imidazole N-atom is also involved in ligation with nickel(II) and both nickel(II) centers have the same chromophore described as NiN5O. The Ni...Ni distances are in the 5.5199(10)–5.5807(15)Å range. Analyses of the magnetic properties of complexes (1), (3) and (4) show that a weak ferromagnetic interaction exists between the two nickel(II) centers. 相似文献
998.
为了探寻电流脉冲泄流时,设备的接地是否有效可靠,用FDTD法分析了脉冲泄流时均一土壤、分层土壤及局部改善土壤的电导率对冲击接地阻抗(TGR)的影响。结果表明:大地电导率对冲击接地阻抗的影响很大;对均一土壤,TGR随大地电导率的增大而减小,大地电导率越大,TGR对接地体的埋深越不敏感。对分层土壤,接地体要埋在大地电导率大的土壤层中,且不要靠近交界面;局部改善大地导电性能对降低TGR效果明显,TGR对改善区域的体积非常敏感,而当电导率大于一定值时,大地电导率的再增加,对TGR的影响不明显。 相似文献
999.
1000.
Diffraction anomaly corresponds to an energy re-distribution in the reflected and transmitted light beams and in different diffraction orders of a grating, which leads to sharp modulations on the transmission and reflection spectra. In gratings sitting on a transparent substrate, this portion of the energy is actually transferred to channels separated from the reflected and transmitted beams. These channels are based on multiple degenerated diffraction processes at the same wavelength as the diffraction anomaly. The spectroscopic response of these channels is sensitive to the change in the environmental refractive index and can be utilized in sensor devices. 相似文献