全文获取类型
收费全文 | 87814篇 |
免费 | 802篇 |
国内免费 | 446篇 |
专业分类
化学 | 31109篇 |
晶体学 | 893篇 |
力学 | 7004篇 |
数学 | 32777篇 |
物理学 | 17279篇 |
出版年
2023年 | 64篇 |
2022年 | 208篇 |
2021年 | 253篇 |
2020年 | 193篇 |
2019年 | 214篇 |
2018年 | 10568篇 |
2017年 | 10353篇 |
2016年 | 6349篇 |
2015年 | 1149篇 |
2014年 | 684篇 |
2013年 | 977篇 |
2012年 | 4575篇 |
2011年 | 11288篇 |
2010年 | 6118篇 |
2009年 | 6430篇 |
2008年 | 7243篇 |
2007年 | 9360篇 |
2006年 | 778篇 |
2005年 | 1810篇 |
2004年 | 1973篇 |
2003年 | 2331篇 |
2002年 | 1372篇 |
2001年 | 473篇 |
2000年 | 474篇 |
1999年 | 297篇 |
1998年 | 275篇 |
1997年 | 233篇 |
1996年 | 303篇 |
1995年 | 209篇 |
1994年 | 161篇 |
1993年 | 158篇 |
1992年 | 121篇 |
1991年 | 116篇 |
1990年 | 105篇 |
1989年 | 106篇 |
1988年 | 87篇 |
1987年 | 71篇 |
1986年 | 68篇 |
1985年 | 77篇 |
1984年 | 65篇 |
1983年 | 59篇 |
1982年 | 65篇 |
1981年 | 60篇 |
1980年 | 63篇 |
1979年 | 62篇 |
1978年 | 56篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
961.
Lawrence JR Glass SV Park SC Nathanson GM 《The journal of physical chemistry. A》2005,109(33):7458-7465
The entry of HCl into 60-68 wt % D(2)SO(4) and HBr into 68 wt % acid containing 0-0.18 M 1-butanol was monitored by measuring the fractions of impinging HCl and HBr molecules that desorb as DCl and DBr after undergoing H --> D exchange within the deuterated acid. The addition of 0.18 M butanol to the acid creates butyl films that reach approximately 80% surface coverage at 213 K. Surprisingly, this butyl film does not impede exchange but instead enhances it: the HCl --> DCl exchange fractions increase from 0.52 to 0.74 for 60 wt % D(2)SO(4) and from 0.14 to 0.27 for 68 wt % D(2)SO(4). HBr --> DBr exchange increases even more sharply, rising from 0.22 to 0.65 for 68 wt % D(2)SO(4). We demonstrate that this enhanced exchange corresponds to enhanced uptake into the butyl-coated acid for HBr and infer this equivalence for HCl. In contrast, the entry probability of the basic molecule CF(3)CH(2)OH exceeds 0.85 at all acid concentrations and is only slightly diminished by the butyl film. The OD groups of surface butanol molecules may assist entry by providing extra interfacial protonation sites for HCl and HBr dissociation. The experiments suggest that short-chain surfactants in sulfuric acid aerosols do not hinder heterogeneous reactions of HCl or HBr with other solute species. 相似文献
962.
V. L Gein E. N. Bezmaternykh L. F. Gein I. V. Krylova 《Chemistry of Heterocyclic Compounds》2004,40(10):1332-1334
It has been shown that 5-aryl-3-arylamino-4-benzoyl-1H-3-pyrrolin-2-ones cyclize in the presence of conc. H2SO4 to give pyrrolo[3,4-b]quinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1543–1545, October, 2004. 相似文献
963.
Comparison
of the fragility index of different eudragit polymers determined by activation
enthalpies
Gabriella Csóka A. Gelencsér Dorottya Kiss Eszter Pásztor I. Klebovich Romána Zelkó 《Journal of Thermal Analysis and Calorimetry》2007,87(2):469-473
The present study aimed to apply fragility
index (m) of polymers in the determination
of the optimal amount of plasticizer in polymer films. The fragility index
of different Eudragit polymers (RS, RL, EPO) was assessed by differential
scanning calorimerty (DSC), applying the Arrhenius connection (logq–1/T
g).
The fragility of Eudragit EPO films proved to be the highest, while in the
case of RS and RL, the increase of the alkyl-chain length caused the increase
of fragility. Studying the effect of plasticizer (triethyl citrate, TEC) on
the m value of Eudragit RL and RS films,
a near linear reduction of the fragility index could be observed between 5–30%
TEC concentration, but above 30%, this value leveled out to constant. 相似文献
964.
Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation. 相似文献
965.
p21Cip/WAF1, an important regulator of cell proliferation, is induced by both p53- and extracellular signal regulated kinase (ERK) pathways. The induction of p21Cip/WAF1 occurs by prolonged activation of the ERKs caused by extracellular stimuli, such as zinc. However, not all the cells appeared to respond to ERK pathway dependent p21Cip/WAF1 induction. Here we investigated the cause of such difference using colorectal cancer cells. p21Cip/WAF1 induction and concomitant reduction of bromodeoxyuridine (BrdU) incorporation were observed by zinc treatment within HT-29 and DLD-1. However, HCT-116 cells with high endogenous p21Cip/WAF1 levels did not show any additional increment of p21Cip/WAF1 levels by zinc treatment and did maintain high BrdU incorporation level. The p21Cip/WAF1 induction by zinc depended upon prolonged activation of extracellular signal regulated kinase (ERK) was not observed in HCT-116 cells. The percentage of BrdU positive cells was 50% higher in p21Cip/WAF1 -/- HCT-116 cells compared to p21Cip/WAF1 +/+ HCT- 116 cells, and no cells induced p21Cip/WAF1 incorporated BrdU in its nucleus, yet confirming the importance of p21Cip/WAF1 induction in anti- proliferation. These results again support that p21Cip/WAF1 induction is a determinant in the regulation of colonic proliferation by the ERK pathway. 相似文献
966.
de Visser SP Shaik S Sharma PK Kumar D Thiel W 《Journal of the American Chemical Society》2003,125(51):15779-15788
The active site of HRP Compound I (Cpd I) is modeled using hybrid density functional theory (UB3LYP). The effects of neighboring amino acids and of environmental polarity are included. The low-lying states have porphyrin radical cationic species (Por(*)(+)). However, since the Por(*)(+) species is a very good electron acceptor, other species, which can be either the ligand or side chain amino acid residues, may participate in electron donation to the Por(*)(+) moiety, thereby making Cpd I behave like a chemical chameleon. Thus, this behavior that was noted before for Cpd I of P450 is apparently much more wide ranging than initially appreciated. Since chemical chameleonic behavior property was found to be expressed not only in the properties of Cpd I itself, but also in its reactivity, the roots of this phenomenon are generalized. A comparative discussion of Cpd I species follows for the enzymes HRP, CcP, APX, CAT (catalase), and P450. 相似文献
967.
Judit E. Puskas Sam W. P. Chan Kimberley B. McAuley Sohel Shaikh Gabor Kaszas 《Journal of polymer science. Part A, Polymer chemistry》2005,43(22):5394-5413
This article is a critical analysis of kinetic dataavailable on carbocationic polymerizations. A survey of published propagation rate constant (kp) data revealed several orders of magnitude differences. In this article, an explanation of this apparent discrepancy is offered with a case study involving the carbocationic polymerization of 2,4,6‐trimethylstyrene (TMS). With the polymerization mechanism originally proposed for this system, kp = 1.35 × 104 L mol?1 s?1 was extracted from experimental data with the Predici polyreaction package. The alternative mechanism yielded kp = 1.01 × 107 L mol?1 s?1, close to that predicted by Mayr's Linear Free Energy Relationship (LFER). We propose that true rate constants can only be obtained from direct competition experiments or from kinetic interpretation based on independently proven mechanisms. The second part of this review discusses critical analysis of the temperature and concentration dependence of various living IB systems. Comparison of the temperature dependence in systems initiated with 2‐ chloro‐2,4, 4‐ trimethylpentane (TMPCl)/TiCl4 from various laboratories yielded of ΔH ~?25 and ?34.5 kJ/mol for high and low TMPCl/TiCl4 ratios, respectively. Aromatic (cumyl‐type) initiators show ΔH ~ ?40 kJ/mol, whereas H2O/TiCl4 in the presence of the strong electron‐ pair donor dimethylacetamide gave ΔH = ?12 kJ/mol. The significant differences indicate different underlying mechanisms with complex elementary reactions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5394–5413, 2005 相似文献
968.
With P(CH3)3 as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH3)3]+ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH3)3]+ species from the first to the second Brönsted acidic site. 相似文献
969.
Young Hyun Cho Wanno Lee Kun Ho Chung Geun Sik Choi Chang Woo Lee 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(3):531-538
The seasonal variation of the 7Be activities in air and the size distribution of the 7Be aerosols were studied by using a continuous air sampler and a five stage cascade impactor. The mean monthly activity level
of 7Be at the Korea Atomic Energy Research Institute (KAERI) site varied from 0.5 to 4.8 Bq·m−3 and revealed a seasonal variation, in which the 7Be activity levels were high in winter and low in summer. The mass size distribution showed a bi-modal distribution with a
higher peak around 0.49 μm and a smaller peak between 3 μm and 7.2 μm. The activity median aerodynamic diameter (AMAD) decreased
with increasing ambient 7Be concentrations. The mean residence times by using a mean growth rate of 0.004 μm·h−1 were estimated to be 2.5–6.4 days. The AMAD has an increasing tendency with higher relative humidity. It seemed that the
high humidity condition facilitated the growth of the aerosol, resulting in increased deposition rates of the aerosols and
the low 7Be content in the surface air. The AMAD of the 7Be aerosols increased with an increasing temperature, but the temperature dependency of AMAD should be explained with geological
and meteorological conditions. 相似文献
970.