全文获取类型
收费全文 | 2943篇 |
免费 | 103篇 |
国内免费 | 13篇 |
专业分类
化学 | 2269篇 |
晶体学 | 28篇 |
力学 | 41篇 |
数学 | 189篇 |
物理学 | 532篇 |
出版年
2023年 | 15篇 |
2021年 | 28篇 |
2020年 | 37篇 |
2019年 | 68篇 |
2018年 | 31篇 |
2017年 | 31篇 |
2016年 | 57篇 |
2015年 | 43篇 |
2014年 | 49篇 |
2013年 | 138篇 |
2012年 | 169篇 |
2011年 | 185篇 |
2010年 | 89篇 |
2009年 | 88篇 |
2008年 | 168篇 |
2007年 | 160篇 |
2006年 | 177篇 |
2005年 | 153篇 |
2004年 | 113篇 |
2003年 | 129篇 |
2002年 | 119篇 |
2001年 | 59篇 |
2000年 | 44篇 |
1999年 | 34篇 |
1998年 | 32篇 |
1997年 | 26篇 |
1996年 | 24篇 |
1995年 | 16篇 |
1994年 | 16篇 |
1993年 | 27篇 |
1992年 | 30篇 |
1991年 | 29篇 |
1990年 | 40篇 |
1989年 | 28篇 |
1988年 | 31篇 |
1987年 | 26篇 |
1986年 | 35篇 |
1985年 | 31篇 |
1984年 | 45篇 |
1983年 | 29篇 |
1982年 | 39篇 |
1981年 | 34篇 |
1980年 | 35篇 |
1979年 | 31篇 |
1978年 | 37篇 |
1977年 | 32篇 |
1976年 | 22篇 |
1975年 | 19篇 |
1974年 | 25篇 |
1973年 | 23篇 |
排序方式: 共有3059条查询结果,搜索用时 265 毫秒
41.
Ionizing radiations, which have already been utilized for the sterilization of medical supplies as well as gas fumigation, should be the final candidate to decontaminate “hybrid” biomaterials containing bio-active materials including enzymes because irradiation induces neither heat nor substances affecting the quality of the materials and our health. In order to check the feasibility of 60Co-gamma rays on these materials, we selected commercial proteases including papain and bromelain hybridized with commercial activated chitosan beads and demonstrated that these enzyme-hybrids suspended in water showed the significant radiation durability of more than twice as much as free enzyme solution at 25-kGy irradiation. Enhanced thermal and storage stability of the enzyme hybrids were not affected by the same dose level of irradiation, either, indicating that commercial irradiation sterilization method is applicable to enzyme hybrids without modification. 相似文献
42.
Hiromu Hayashi 《Catalysis Surveys from Japan》1999,3(1):43-52
Additive telluromolybdates, MoO3·2TeO2 and MIIO·TeO2·MoO3 (MIITeMoO6; MII = Co, Mn, Zn), converted ethyl lactate selectively to pyruvate in a vaporphase fixedbed flow system at 250–300 °C. A synergy in activity was observed for binary TeO2–MoO3, and crystalline Te2MoO7 was suggested as the active species. The Rietveld analysis of powder XRD patterns of ternary CoTeMoO6 revealed the layer structure quite different from that of the reference Te2MoO7, but tellurium was again located adjacent to molybdenum linked through lattice oxygen. 相似文献
43.
The photoisomerization properties of tris(bipyridine)cobalt complexes containing six or three azobenzene moieties, namely, [Co(II)(dmAB)3](BF4)2 [dmAB = 4,4'-bis[3'-(4'-tolylazo)phenyl]-2,2'-bipyridine], [Co(III)(dmAB)3](BF4)3, [Co(II)(mAB)3](BF4)2 [mAB = 4-[3' '-(4' '-tolylazo)phenyl]-2,2'-bipyridine], and [Co(III)(dmAB)3](BF4)3, derived from the effect of gathering azobenzenes in one molecule and the effect of the cobalt(II) or cobalt(III) ion were investigated using UV-vis absorption spectroscopy, femtosecond transient spectroscopy, and 1H NMR spectroscopy. In the photostationary state of these four complexes, nearly 50% of the trans-azobenzene moieties of the Co(II) complexes were converted to the cis isomer, and nearly 10% of the trans-azobenzene moieties of the Co(III) complexes isomerized to the cis isomer, implying that the cis isomer ratio in the photostationary state upon irradiation at 365 nm is controlled not by the number of azobenzene moieties in one molecule but rather by the oxidation state of the cobalt ions. The femtosecond transient absorption spectra of the ligands and the complexes suggested that the photoexcited states of the azobenzene moieties in the Co(III) complexes were strongly deactivated by electron transfer from the azobenzene moiety to the cobalt center to form an azobenzene radical cation and a Co(II) center. The cooperation among the photochemical structural changes of six azobenzene moieties in [Co(II)(dmAB)3](BF4)2 was investigated with 1H NMR spectroscopy. The time-course change in the 1H NMR signals of the methyl protons indicated that each azobenzene moiety in [Co(II)(dmAB)3](BF4)2 isomerized to a cis isomer with a random probability of 50% and without interactions among the azobenzene moieties. 相似文献
44.
Chiral β-dimethylaminoalkylphosphines were prepared starting with amino acids, (S)-alanine, (S)-phenylalanine, (R)-phenylglycine, (S)-valine, and (R)-tert-leucine. The chiral phosphines were found to be highly efficient ligands for a nickel catalyzed asymmetric Grignard cross-coupling reaction (38~94% optical yield). 相似文献
45.
Kakiuchi F Tsuchiya K Matsumoto M Mizushima E Chatani N 《Journal of the American Chemical Society》2004,126(40):12792-12793
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction. 相似文献
46.
To elucidate the mechanism(s) of the relieving effect of saline on cephaloridine (CER) nephrotoxicity, rats were given CER in equal quantity (1 g/kg body weight; i.v.), but at two different concentrations (4 and 25%) in saline. Urinary excretion of glucose, which was investigated as an index for renal proximal tubular injury, revealed that the renal damage was less in the 4% CER 25 ml/kg group than in the 25% CER 4 ml/kg group. As to urinary excretions of CER, sodium, potassium and water, no significant differences were observed between the two groups in the first 2 h, but chloride in the 4% CER 25 ml/kg group showed higher values than in the 25% CER 4 ml/kg group. Plasma concentrations of sodium, potassium, chloride and CER, did not show any definite distinctions between the two groups. At the time-point of 20 min after the CER administration, renal CER content was significantly lower in the 4% CER 25 ml/kg group than in the 25% CER 4 ml/kg group. These results suggest that the sodium ion which is needed for cellular trapping of CER is competitively expended for cellular entry of the chloride ion in the kidney, and that the relieving effect of the saline on CER nephrotoxicity is ascribable to the loaded quantity of chloride ion. 相似文献
47.
Puzenko A Hayashi Y Ryabov YE Balin I Feldman Y Kaatze U Behrends R 《The journal of physical chemistry. B》2005,109(12):6031-6035
We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed. 相似文献
48.
Katsuki Kusakabe Kiyotaka IchikiJun-ichiro Hayashi Hideaki MaedaShigeharu Morooka 《Journal of membrane science》1996
Silica-polyimide microcomposite membranes were prepared on γ-alumina-coated α-alumina support tubes, and their gas permeation properties were evaluated with He, N2 and CO2. Smoothing of the substrate surface and hybridization of silica and polyamic acid were both effective to form defect-free thin composite membranes. The CO2 permeance of a membrane with a silica content of 68 wt% was one order of magnitude higher than that of a polyimide membrane having the same thickness. The permselectivity of CO2 to N2 was 30 at 30°C and 13 at 100°C. Contributions of the silica and polyimide phases to permeance of the composite membrane were analyzed with a two-phase permeation model. The effective thickness of the rate-controlling polyimide phase was less than one-tenth of the total thickness of the silica-polyimide membrane. 相似文献
49.
Masahiro Irie Senzo Sasaoka Yukio Yamamoto Koichiro Hayashi 《Journal of polymer science. Part A, Polymer chemistry》1979,17(3):815-820
Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above ?36°C) and plastic crystal (between ?36 and ?81°C) phases. A quantum yield of monomer consumption as high as 8 × 103 was observed in the plastic crystal phase. Below ?81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed. 相似文献
50.
[reaction: see text] A formal total synthesis of the sex attractant of male dried bean beetle, methyl (R,E)-(-)-tetradeca-2,4,5-trienoate, was achieved by a new efficient route utilizing the Pd-catalyzed asymmetric allene synthesis reaction. It was found that the atropisomeric biaryl bisphosphine (R)-segphos showed better enantioselectivity than (R)-binap in the Pd-catalyzed reaction for preparing alkyl-substituted axially chiral allenes. 相似文献