全文获取类型
收费全文 | 6173篇 |
免费 | 226篇 |
国内免费 | 57篇 |
专业分类
化学 | 4212篇 |
晶体学 | 46篇 |
力学 | 152篇 |
数学 | 1088篇 |
物理学 | 958篇 |
出版年
2023年 | 48篇 |
2022年 | 99篇 |
2021年 | 141篇 |
2020年 | 122篇 |
2019年 | 98篇 |
2018年 | 101篇 |
2017年 | 87篇 |
2016年 | 193篇 |
2015年 | 190篇 |
2014年 | 230篇 |
2013年 | 395篇 |
2012年 | 367篇 |
2011年 | 493篇 |
2010年 | 329篇 |
2009年 | 271篇 |
2008年 | 387篇 |
2007年 | 390篇 |
2006年 | 311篇 |
2005年 | 306篇 |
2004年 | 273篇 |
2003年 | 214篇 |
2002年 | 208篇 |
2001年 | 89篇 |
2000年 | 68篇 |
1999年 | 63篇 |
1998年 | 50篇 |
1997年 | 58篇 |
1996年 | 69篇 |
1995年 | 48篇 |
1994年 | 48篇 |
1993年 | 33篇 |
1992年 | 34篇 |
1991年 | 23篇 |
1990年 | 21篇 |
1989年 | 29篇 |
1987年 | 27篇 |
1986年 | 24篇 |
1985年 | 41篇 |
1984年 | 42篇 |
1983年 | 30篇 |
1982年 | 38篇 |
1981年 | 38篇 |
1980年 | 26篇 |
1979年 | 32篇 |
1978年 | 31篇 |
1977年 | 32篇 |
1976年 | 19篇 |
1975年 | 19篇 |
1974年 | 17篇 |
1973年 | 25篇 |
排序方式: 共有6456条查询结果,搜索用时 15 毫秒
991.
Del Bene JE Elguero J Alkorta I Yañez M Mó O 《The journal of physical chemistry. A》2007,111(3):419-421
This paper reports computed NMR spectral data for the diazaborole anion (C2H4B1N2-) and the corresponding neutral five-membered rings with B-H (C2H5B1N2, diazaborole) and B-Li (C2H4B1Li1N2, Li-diazaborole) bonds, which are the central moieties of newly synthesized nucleophilic organoboryl five-membered rings, recently reported by Segawa et al. (Science 2006, 314, 113). Both spin-spin coupling constants and chemical shifts were obtained using high-level ab initio calculations. These data are a necessary complement to the very scarce experimental information available. 相似文献
992.
A high-pressure turbulent flow reactor coupled with a chemical ionization mass-spectrometer was used to determine the branching ratio of the HO(2) + NO reaction: HO(2) + NO --> OH + NO(2) (1a), HO(2) + NO --> HNO(3) (1b). The branching ratio, beta = k(1b)/k(1a), was derived from the measurements of "chemically amplified" concentrations of the NO(2) and HNO(3) products in the presence of O(2) and CO. The pressure and temperature dependence of beta was determined in the pressure range of 72-600 Torr of N(2) carrier gas between 323 and 223 K. At each pressure, the branching ratio was found to increase with the decrease of temperature, the increase becoming less pronounced with the increase of pressure. In the 298-223 K range, the data could be fitted by the expression: beta(T,P) = (530 +/- 10)/T(K) + (6.4 +/- 1.3) x 10(-4)P(Torr) - (1.73 +/- 0.07), giving beta approximately 0.5% near the Earth's surface (298 K, 760 Torr) and 0.8% in the tropopause region (220 K, 200 Torr). The atmospheric implication of these results is briefly discussed. 相似文献
993.
Alvarez-Aguilar C Enríquez-Ramírez ML Figueroa-Nuñez B Gómez-García A Rodríguez-Ayala E Morán-Moguel C Farías-Rodríguez VM Mino-León D López-Meza JE 《Experimental & molecular medicine》2007,39(3):327-334
Metabolic Syndrome (MS) is recognized as a cluster of cardiovascular risk factors. All components of MS have a genetic base. Genes of the renin angiotensin system are potential candidate genes for MS. We investigated whether angiotensin converting enzyme (ACE) gene polymorphism increases susceptibility to MS as an entity in a Mexican population. In a cross-sectional study, 514 individuals were studied including 245 patients with MS and 269 subjects without MS criteria. ACE gene polymorphism was detected using PCR. MS was defined according to The National Cholesterol Education Program Expert Panel on Detection, Evaluation, and Treatment of High Blood Cholesterol in Adults (Adult Treatment Panel III) criteria, except that the raised fasting plasma glucose 相似文献
994.
Freire F Seco JM Quiñoá E Riguera R 《Chemical communications (Cambridge, England)》2007,(14):1456-1458
The absolute configuration of beta-chiral primary alcohols devoid of observable hydrogens on one of the beta-substituents at the asymmetric carbon (L(1)/L(2)) can be determined by comparison of the (1)H NMR of their (R)- and (S)-9-AMA ester derivatives and analysis of the Deltadelta(RS) for the L substituent and the Cbeta-H. 相似文献
995.
Janetzky M Rödel E Pietzonka C Müller U Ressler T Harbrecht B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9882-9891
Pd(4)Br(4)Te(3) was prepared from Pd, Te, and PdBr(2) at 700 K. Its structure was determined by single-crystal X-ray diffraction to be triclinic, P$\bar 1$, Pearson symbol aP22; a=842.5(2), b=845.0(3), c=864.8(3) pm; alpha=82.55(3), beta=73.36(2), gamma=88.80(2) degrees ; Z=2. The Br and Te atoms are arranged according to the motif of cubic closest-packed spheres in which every 15th position is vacant; the Pd atoms occupy 8/15 of the octahedral voids. The symmetry relations with the packing of spheres are derived. Prominent structural units are hollow cuboctahedral [(PdBrTe)(6)] units, the Pd atoms are positioned near the centers of the square faces of the Br(6)Te(6) cuboctahedra; the cuboctahedra and double-octahedral Pd(2)Br(4)Te(6) units are connected to strands by sharing triangular Te(3) faces. The strands are condensed by common Br atoms into layered assemblies. Conspicuously close Te--Te contacts in the Te(3) triangles indicate attractive Te--Te interactions. The valence puzzle is resolved by the formula Pd(+II)(4)Br(-I)(4)Te(-4/3)(3). Positive Te--Te Mulliken orbital populations and the Pd--K, Br--K, and Te--L(III) XANES spectra of Pd(4)Br(4)Te(3) referenced to the spectra of PdBr(2), K(2)PdBr(6), PdTe, and PdTe(2) are in accord with attractive Te--Te interactions. The measured semiconducting and diamagnetic properties are compatible with the derived picture of chemical bonding in Pd(4)Br(4)Te(3). 相似文献
996.
Paneque M Posadas CM Poveda ML Rendón N Alvarez E Mereiter K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(18):5160-5172
The reaction of the bis(ethylene) complex [Tp(Me(2) )Ir(C(2)H(4))(2)] (1) (Tp(Me(2) ): hydrotris(3,5-dimethylpyrazolyl)borate) with two equivalents of dimethyl acetylenedicarboxylate (DMAD) in CH(2)Cl(2) at 25 degrees C gives the hydride-alkenyl species [Tp(Me(2) )IrH{C(R)=C(R)C(R)=C(R)CH=CH(2)}] (2, R: CO(2)Me) in high yield. A careful study of this system has established the active role of a number of intermediates en route to producing 2. The first of these is the iridium(I) complex [Tp(Me(2) )Ir(C(2)H(4))(DMAD)] (4) formed by substitution of one of the ethylene ligands in 1 by a molecule of DMAD. Complex 4 reacts further with another equivalent of the alkyne to give the unsaturated metallacyclopentadiene [Tp(Me(2) )Ir{C(R)=C(R)C(R)=C(R)}], which can be trapped by added water to give adduct 7, or can react with the C(2)H(4) present in solution generating complex 2. This last step has been shown to proceed by insertion of ethylene into one of the Ir--C bonds of the metallacyclopentadiene and subsequent beta-H elimination. Complex 1 reacts sequentially with one equivalent of DMAD and one equivalent of methyl propiolate (MP) in the presence of water, with regioselective formation of the nonsymmetric iridacyclopentadiene [Tp(Me(2) )Ir{C(R)=C(R)C(H)=C(R)}(H(2)O)] (9). Complex 9 reacts with ethylene giving a hydride-alkenyl complex 10, related to 2, in which the C(2)H(4) has inserted regiospecifically into the Ir--C(R) bond that bears the CH functionality. Heating solutions of either 2 or 10 in CH(2)Cl(2) allows the formation of the allyl species 3 or 11, respectively, by simple stereoselective migration of the hydride ligand to the Calpha alkenyl carbon atom and concomitant bond reorganization of the resulting organic chain. All the compounds described herein have been characterized by microanalysis, IR and NMR spectroscopy, and for the case of 3, 7, 7CO, 8NCMe, 9, 9NCMe, and 10, also by single-crystal X-ray diffraction studies. 相似文献
997.
Jiménez-González L García-Muñoz S Alvarez-Corral M Muñoz-Dorado M Rodríguez-García I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(2):557-568
The condensation of 2,3-dihydrobenzoxasilepins with aromatic aldehydes in the presence of boron trifluoride to form 2,3-dihydrobenzofurans shows a level of diastereoselection which is a function of the electronic nature of the aldehyde and the polarity of the solvent. The study of the mechanism of the reaction demonstrated that it proceeds through a ring-opened allylfluorosilane, which is stable enough to be isolated and characterized. 相似文献
998.
Nunes JP Figueira MJ Belo D Santos IC Ribeiro B Lopes EB Henriques RT Vidal-Gancedo J Veciana J Rovira C Almeida M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9841-9849
The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals. 相似文献
999.
Walmsley JA Zhu S Matilla A Donowick TG Cramp JE Tercero JM Dalrymple T 《Inorganic chemistry》2007,46(23):9945-9953
Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, and those species containing trimetylsilyl and t-butyl groups bonded the most strongly. The size of the central cavity of the [Pd(en)(5'GMP)]6 host has been estimated to be 5.2 A. Formation of the host-guest complex caused a large upfield shift (Deltadelta) of 2.5-2.9 ppm in the 1H NMR spectrum of the most highly affected guest protons, which were those in closest proximity to the guanine nucleobases. NOESY spectra were used to determine the interaction sites between the host and the guest. Apparent association constants determined at 26 degrees C and pD 5.4 for the [Pd(en)(5'GMP)]6-DSS and [Pd(en)(5'GMP)]6-t-butanol systems, where DSS is 3-(trimethylsilyl)-1-propanesulfonate anion, were 1.36+/-0.11x10(4) and 2.74+/-0.95x10(4) M(-3/2), respectively. The Pd(dapol)-5'GMP system forms hexameric host-guest complexes, similar in nature to those of the Pd(en)-5'GMP system. The molecular and crystal structures of Pd(dapol)Cl2 are also reported. 相似文献
1000.
Synthesis, structure determination, and magnetic properties are reported for the metastable and crystal-chemically isotypic phases cobalt carbodiimide, CoNCN, and nickel carbodiimide, NiNCN, adopting the hexagonal system and space group P63/mmc (NiAs type) with interatomic distances of Co-N = 2.17 Angstrom and Ni-N = 2.12 Angstrom and an octahedral coordination of the transition-metal ions; the NCN(2-) units reveal the carbodiimide shape with two C=N double bonds. The low-susceptibility data go back to strong antiferromagnetic spin-spin coupling, similar to the behavior of the electronically related oxides CoO and NiO. 相似文献