全文获取类型
收费全文 | 3624篇 |
免费 | 228篇 |
国内免费 | 155篇 |
专业分类
化学 | 2697篇 |
晶体学 | 48篇 |
力学 | 86篇 |
综合类 | 12篇 |
数学 | 179篇 |
物理学 | 985篇 |
出版年
2023年 | 18篇 |
2022年 | 27篇 |
2021年 | 53篇 |
2020年 | 69篇 |
2019年 | 79篇 |
2018年 | 73篇 |
2017年 | 50篇 |
2016年 | 98篇 |
2015年 | 97篇 |
2014年 | 120篇 |
2013年 | 203篇 |
2012年 | 196篇 |
2011年 | 226篇 |
2010年 | 124篇 |
2009年 | 142篇 |
2008年 | 217篇 |
2007年 | 165篇 |
2006年 | 198篇 |
2005年 | 182篇 |
2004年 | 199篇 |
2003年 | 157篇 |
2002年 | 166篇 |
2001年 | 125篇 |
2000年 | 80篇 |
1999年 | 91篇 |
1998年 | 41篇 |
1997年 | 35篇 |
1996年 | 50篇 |
1995年 | 48篇 |
1994年 | 42篇 |
1993年 | 33篇 |
1992年 | 55篇 |
1991年 | 49篇 |
1990年 | 28篇 |
1989年 | 34篇 |
1988年 | 21篇 |
1987年 | 34篇 |
1986年 | 36篇 |
1985年 | 34篇 |
1984年 | 21篇 |
1983年 | 18篇 |
1982年 | 26篇 |
1981年 | 24篇 |
1980年 | 31篇 |
1979年 | 20篇 |
1978年 | 20篇 |
1977年 | 17篇 |
1975年 | 21篇 |
1974年 | 20篇 |
1973年 | 26篇 |
排序方式: 共有4007条查询结果,搜索用时 15 毫秒
61.
Kawasaki H Sasaki A Kawashima T Sasaki S Kakehashi R Yamashita I Fukada K Kato T Maeda H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5731-5737
Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain. 相似文献
62.
A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]2·4H2O [H2saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr2O2 unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S1=S2=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm‐1, and zJ' =0.18(3)cm‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex. 相似文献
63.
Otaka A Yukimasa A Watanabe J Sasaki Y Oishi S Tamamura H Fujii N 《Chemical communications (Cambridge, England)》2003,(15):1834-1835
Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields. 相似文献
64.
Chiral quaternary ammonium salts derived from cinchonidine have been applied to catalyze the stereoselective iodolactonizations of trans-5-aryl-4-pentenoic acids leading to a mixture of two regioselectively iodolactonized products with fair to excellent yield (37-98%) and moderate enantioselectivity (exo = 42.0% ee, endo = 31.0% ee) under mild conditions. This work is the first example of asymmetric iodolactonization reaction in the presence of less than a stoichiometric amount of chiral reagent. 相似文献
65.
Oguchi T Tozuka Y Hanawa T Mizutani M Sasaki N Limmatvapirat S Yamamoto K 《Chemical & pharmaceutical bulletin》2002,50(7):887-891
The solid-state complexation between cholic acid (CA) and either methyl p-hydroxybenzoate (MPB) or ibuprofen (IBP) was investigated. Powder X-ray diffractometry, IR spectroscopy and thermal analysis suggested the complex formation between CA and MPB as well as between CA and IBP by co-grinding method. The stoichiometry of CA-MPB was 1 : 1 while that of CA-IBP was 2 : 1, reflecting the effect of guest size on complex formation. The guest compounds were assumed to be included in the channel of complexes formed by hydrogen bonds among CA molecules. 相似文献
66.
Ozone was tested as an alternative digestion/oxidation system to the permanganate/peroxidisulfate currently used in the cold vapor mercury method. The results indicate that the digestion of comparable size samples to the 'Standard Method' was complete in less than 2 min. A 0.5 ml (10 ppb) sample size was completely oxidized in less than 30 s. The batch system used produced a limit of detection (LOD) for mercury(II) chloride, methylmercury chloride, and phenylmercury acetate of about 0.5 ppb. 相似文献
67.
Meso-四(对-磺基苯基)卟啉光度法测定螺旋藻中的痕量锌 总被引:5,自引:0,他引:5
在pH=4.5的乙酸-乙酸钠缓冲介质中,锌和meso-四-(对磺基苯基)卟啉生成1:l的黄色配合物,λmax=421nm,ε=4.34×105L·mol-1·cm-1。该法可不经分离直接测定螺旋藻中的锌,结果满意。 相似文献
68.
Otaka A Watanabe J Yukimasa A Sasaki Y Watanabe H Kinoshita T Oishi S Tamamura H Fujii N 《The Journal of organic chemistry》2004,69(5):1634-1645
A samarium diiodide (SmI(2))-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI(2) proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to alpha-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI(2)-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF[double bond]CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the alpha-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities. 相似文献
69.
Sasaki M Kawanishi E Nakai Y Matsumoto T Yamaguchi K Takeda K 《The Journal of organic chemistry》2003,68(24):9330-9339
Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond. 相似文献
70.
Osamu Sangen Singo Masuda Hidehiko Nakano Kazusige Yamana Kenichi Sasaki Naoki Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):1171-1175
A new synthetic pathway of A–B–A tri-block copolyether which is composed of a hydrophilic poly(oxyethylene) unit as an A part and a hydrophobic poly(oxy-2-methyl-trimethylene) unit as a B part is proposed. Telechelic α-tosyl-ω-tosyloxypoly(oxy-2-methyl-trimethylene) derived from tosylation of poly(oxy-2-methyl-trimethylene glycol) (PMTG) was allowed to react with poly(ethylene glycol) (PEG) in the presence of sodium hydroxide. Tg of the resulting A–B–A tri-block copolyether (PEMG) (M?n = 1600) was ?72°C and its specific gravity [D415] was 1.055. 相似文献