全文获取类型
收费全文 | 35544篇 |
免费 | 9576篇 |
国内免费 | 1399篇 |
专业分类
化学 | 41397篇 |
晶体学 | 326篇 |
力学 | 426篇 |
数学 | 2052篇 |
物理学 | 2318篇 |
出版年
2023年 | 23篇 |
2022年 | 58篇 |
2021年 | 206篇 |
2020年 | 1251篇 |
2019年 | 2591篇 |
2018年 | 1026篇 |
2017年 | 664篇 |
2016年 | 3379篇 |
2015年 | 3532篇 |
2014年 | 3440篇 |
2013年 | 4100篇 |
2012年 | 2931篇 |
2011年 | 2151篇 |
2010年 | 2860篇 |
2009年 | 2813篇 |
2008年 | 2368篇 |
2007年 | 1753篇 |
2006年 | 1463篇 |
2005年 | 1628篇 |
2004年 | 1436篇 |
2003年 | 1332篇 |
2002年 | 2005篇 |
2001年 | 1361篇 |
2000年 | 1288篇 |
1999年 | 375篇 |
1998年 | 50篇 |
1997年 | 45篇 |
1996年 | 40篇 |
1995年 | 26篇 |
1994年 | 19篇 |
1993年 | 17篇 |
1992年 | 18篇 |
1991年 | 22篇 |
1990年 | 13篇 |
1989年 | 17篇 |
1988年 | 14篇 |
1987年 | 23篇 |
1986年 | 9篇 |
1985年 | 23篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 18篇 |
1981年 | 15篇 |
1980年 | 15篇 |
1979年 | 15篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
941.
The two new compounds [Fe(tren)]FeSbS4 ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)2]Fe2Sb4S10 ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe3+ is part of a [2FeIII‐2S] cluster which is often found in ferredoxines. In addition, Fe2+ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe2+ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe2+ ion is isolated. In both compounds the primary SbS3 units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS4 was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step. 相似文献
942.
A series of new, 2‐substituted 3‐aryl‐8,9,10,11‐tetrahydro‐5‐methyl[1]benzothieno[3′,2′ : 5,6]pyrido[4,3‐d]pyrimidin‐4(3H)‐ones, compounds 5a – q , were designed and synthesized via the aza‐Wittig reaction as the key step. The iminophosphorane 1 reacted with phenyl isocyanate (or 4‐chlorophenyl isocyanate) to the carbodiimide 4 , which was cyclized to 5 upon addition of different amines, EtOH, or phenols in the presence of a catalytic amount of EtONa or K2CO3 (Schemes 1 and 2). The structures of compounds 5 were confirmed by IR, 1H‐ and 13C‐NMR, EI‐MS, elemental analyses, and, in the case of 5l , by single‐crystal X‐ray diffraction (Figure). 相似文献
943.
Xiao‐Hong Wen R.‐K. Li C.‐T. Chen 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(3):i21-i23
Single crystals of a new rubdidium beryllium borate, RbBe4(BO3)3, have been obtained by spontaneous nucleation from a high‐temperature melt. This new orthorhombic (Pnma) structure type contains [Be2BO4]− rings, made of two BeO4 tetrahedra and one BO3 triangle, which constitute the basic structural units. The m plane runs through the B and one of the O atoms and intersects the ring. These rings form chains in the a direction, which are connected in the b and c directions to form zeolite‐type cages in which the Rb+ cations are located, at sites of m symmetry. 相似文献
944.
A potential energy surface for the ground electronic state of the Ar-HI van der Waals complex is calculated at the coupled-cluster with single and double excitations and a noniterative perturbation treatment of triple excitations [CCSD(T)] level of theory. Calculations are performed using for the iodine atom a correlation consistent triple-zeta valence basis set in conjunction with large-core Stuttgart-Dresden-Bonn relativistic pseudopotential, whereas specific augmented correlation consistent basis sets are employed for the H and Ar atoms supplemented with an additional set of bond functions. In agreement with previous studies, the equilibrium structure is found to be linear Ar-I-H, with a well depth of 205.38 cm(-1). Another two secondary minima are also predicted at a linear and bent Ar-H-I configurations with well depths of 153.57 and 151.57 cm(-1), respectively. The parametrized CCSD(T) potential is used to calculate rovibrational bound states of Ar-HI/Ar-DI complexes, and the vibrationally averaged structures of the different isomers are determined. Spectroscopic constants are also computed from the CCSD(T) surface and their comparison with available experimental data demonstrates the quality of the present surface in the corresponding configuration regions. 相似文献
945.
Eduardo Corts Cortas Miryan Adaya Baos Olivia García‐Mellado De Corts 《Journal of heterocyclic chemistry》2004,41(2):277-280
A new synthesis to obtain eleven novel derivatives of 11‐[(o‐ m‐ and p‐substituted)‐phenyl]‐8‐chloro‐3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐1H‐dibenzo[b,e][1,4]diazepin‐1‐ones with possible pharmacological activity in the central nervous system in two efficient steps has been developed. The final products were obtained by condensation and cyclization between 3‐[4‐chloro‐1,2‐phenylenediamine]‐5,5‐dimethyl‐2‐cyclohexenone with (o‐ m‐ and p‐substituted)benzaldehyde. The structure of all products was corroborated by ir, 1H‐nmr, 13C‐nmr and high resolution in ms. 相似文献
946.
Jian Zhang Zhao‐Ji Li Yi‐Hang Wen Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《无机化学与普通化学杂志》2004,630(15):2731-2735
Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C4H4O4)·1/4H2O ( 1 ) and Cu(2, 2′‐bpy)(C4H4O4)0.5(NO3)(H2O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) Å3, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) Å3, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the CuII atom adopts a distorted octahedral in which the CuII atoms are bridged by two H2O molecules into an infinite zigzag chain, [Cu2(H2O)2(C4H4O4)]n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure. 相似文献
947.
Jeong Hyun Yeum Byung Chul Ji Chul Joo Lee Ji Youl Lee Sang‐Seob Lee Sam Soo Kim Joon Ho Kim Won Seok Lyoo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1103-1111
To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (Pn) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with Pn = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with Pn = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002 相似文献
948.
Mohammad Abul‐Haj Miguel Quirs Juan M. Salas 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):934-935
The title compound, [Ni(NCS)2(C5H4N4O)2(H2O)2], crystallizes in the triclinic space group P. The molecular unit contains two neutral molecules of 4,5‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidin‐5‐one (5HtpO) coordinated through the N atom in position 3, two thiocyanate ligands coordinated through their N atoms and two water molecules completing an octahedral environment around the NiII ion, which lies on a centre of inversion. The structure is stabilized by hydrogen bonding. Distances in the coordination sphere are Ni—N3(5HtpO) 2.132 (2), Ni—O(water) 2.085 (2) and Ni—N(thiocyanato) 2.040 (2) Å. 相似文献
949.
The polyphenolic profiles and antioxidant effects of Agastache rugosa Kuntze (Banga) flower,leaf, stem and root
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yun‐Hi Kim Won Sup Lee Soo Jung Lee Jong Sung Jin A. M. Abd El‐Aty Ho‐Chul Shin Jae‐Han Shim Sung Chul Shin 《Biomedical chromatography : BMC》2016,30(2):225-231
Agastache rugosa Kuntze (Korean mint) is used as a spice and in folk medicine in East Asia. The present study identified a total of 18 polyphenols from the flower, leaf, stem and roots of this plant using high‐performance liquid chromatography–tandem mass spectrometry. Fourteen of these compounds had not previously been identified in these plant tissues. Each polyphenol was validated in comparison with external calibration curves constructed using structurally related compounds, with determination coefficients >0.9993. The limits of detection and quantification were 0.092–0.650 and 0.307–2.167 mg/L, respectively. Recoveries of 61.92–116.44% were observed at two spiking levels, with 0.91–11% precision, expressed as relative standard deviation (except anthraquinone spiked at 10 mg/L). Hydroxycinnamic acid was the most abundant compound in the root, while the flowers showed the highest total flavonoid level. Antioxidant activities, determined in terms of reducing power, Fe2+ chelating activity and the radical scavenging activities using α,α‐diphenyl‐β‐picrylhydrazyl and 2‐2?‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid, increased in a concentration‐dependent manner; the highest activity was identified in the stems, followed by leaves > flowers > roots. These findings indicate that A. rugosa is a good source of bioactive compounds and can be used as a functional food. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
950.
Synthesis,structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
A series of mononuclear half‐sandwich cyclometallated iridium complexes with Schiff base ligands were synthesized in good yields. Five air‐stable C,N‐chelate mode complexes were obtained smoothly through metal‐mediated C─H bond activation. Treatments of dimeric metal complexes [Cp*IrCl2]2 with ligands L1–L5 afforded the corresponding C,N‐chelate mononuclear half‐sandwich iridium(III) complexes 1 – 5 . These iridium complexes exhibit high catalytic activity for norbornene polymerization. Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization process. All complexes were characterized using infrared and NMR spectroscopies and elemental analysis. Molecular structures of complexes 1 , 2 and 5 were further confirmed using single‐crystal X‐ray analysis. 相似文献