全文获取类型
收费全文 | 675篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 419篇 |
晶体学 | 15篇 |
力学 | 11篇 |
数学 | 95篇 |
物理学 | 150篇 |
出版年
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 9篇 |
2020年 | 25篇 |
2019年 | 19篇 |
2018年 | 15篇 |
2017年 | 11篇 |
2016年 | 20篇 |
2015年 | 12篇 |
2014年 | 20篇 |
2013年 | 60篇 |
2012年 | 48篇 |
2011年 | 44篇 |
2010年 | 34篇 |
2009年 | 38篇 |
2008年 | 38篇 |
2007年 | 36篇 |
2006年 | 25篇 |
2005年 | 26篇 |
2004年 | 17篇 |
2003年 | 17篇 |
2002年 | 17篇 |
2001年 | 17篇 |
2000年 | 5篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1995年 | 10篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 6篇 |
1958年 | 1篇 |
排序方式: 共有690条查询结果,搜索用时 15 毫秒
681.
Katrin Meier Raul Cardoso‐Gil Walter Schnelle Helge Rosner Ulrich Burkhardt Ulrich Schwarz PD Dr. 《无机化学与普通化学杂志》2010,636(8):1466-1473
A series of isotypic rare‐earth metal pentagermanides including the new compound TbGe5 were prepared by high‐pressure synthesis. They crystallize in the orthorhombic space group Immm [No. 71; a = 395.70(9) pm; b = 611.1(2) pm, and c = 983.6(3) pm for TbGe5]. The crystal structure is isotypic to LaGe5 and consists of puckered germanium slabs, which sandwich a second germanium species and the rare‐earth metal atoms. At ambient pressure, the thermal decomposition of the phases REGe5 (RE = La, Nd, Sm, Gd, and Tb) proceeds via discrete intermediate steps into Ge(cF8) and thermodynamically stable germanium‐poorer phases. The investigated compounds REGe5 are paramagnetic metallic conductors, which order antiferromagnetically at low temperatures. Specific heat measurements reveal that the superconducting state of LaGe5 below Tc = 7.1(1) K is characterized by a critical field of μ0Hc2 = 0.2 T and weak electron‐phonon coupling. Density‐functional based band‐structure calculations yield a very similar electronic structure for all the isotypic REGe5 compounds. Besides a slight increase in the width of the valence band for smaller RE atoms, only minor differences are found for the two different germanium environments. 相似文献
682.
Shubham Vyas Jacek Kubicki Hoi Ling Luk Yunlong Zhang Nina P. Gritsan Christopher M. Hadad Matthew S. Platz 《Journal of Physical Organic Chemistry》2012,25(8):693-703
The photochemistry of pivaloyl, benzoyl, 4‐phenylbenzoyl, and 2‐anthroyl azides has been studied using femtosecond (fs) time‐resolved infrared (TRIR) and UV–vis spectroscopy and interpreted with the aid of computational chemistry. Density functional theory calculations revealed a significant difference in the nature of the lowest singlet excited state for these carbonyl azides. The lowest singlet excited states (S1) of p‐phenylbenzoyl and 2‐anthroyl azides are (π,π*) in nature, while the pivaloyl and benzoyl azides S1 states involve (n,π*) excitations. Nevertheless, for all acyl azides studied here, a similar, and intense, IR band at about 2100 cm?1 has been detected in the ultrafast TRIR experiments following 270 nm excitation. These bands were shifted to lower energy by about 100 cm?1 relative to the N3 stretching mode for the ground states of these azides. These 2100 cm?1 vibrational bands were assigned to the S1 states of acyl azides in agreement with density functional theory calculations. The decay of the acyl azide S1 states was described by bi‐exponential functions. The fast component was attributed to the decay of the hot S1 state and the longer component to the decay of the thermally relaxed S1 state. A strong and broad transient absorption in the 350–650 nm spectral range was observed in the fs UV–vis experiments for p‐phenylbenzoyl and 2‐anthroyl azides. The carrier of this absorption also decayed bi‐exponentially, and the time constants were in excellent agreement with those found in the fs TRIR experiments. The slow component of the S1 state decay was found to be dependent on the solvent polarity. When the lifetime of the acyl azide S1 state is substantially longer than the time constant for vibrational cooling of nascent (hot) isocyanate, the correlation between the S1 decay and isocyanate formation was clear. The 270 nm excitation populates the Sn (n ≥ 2) states of these acyl azides. It was established that a hot nitrene is produced more efficiently from both the Sn and hot S1 states than from the relaxed S1 state of these acyl azides. Thus, time‐resolved study provides direct experimental evidence that the S1 state is the precursor of nitrene only when the S1 state is pumped directly and when the S1 state lifetime is longer than the time constant of vibrational cooling of the newborn nitrene. All of these results are consistent with the data obtained recently for 2‐napththoyl azide. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
683.
Sivaramakrishnan Muthukrishnan Vivekanand S. Shete Toby T. Sanan Shubham Vyas Shameema Oottikkal Lauren M. Porter Thomas J. Magliery Christopher M. Hadad 《Journal of Physical Organic Chemistry》2012,25(12):1247-1260
We designed, synthesized, and screened a library of analogs of the organophosphate pesticide metabolite paraoxon against a recombinant variant of human serum paraoxonase‐1. Alterations of both the aryloxy leaving group and the retained alkyl chains of paraoxon analogs resulted in substantial changes to binding and hydrolysis, as measured directly by spectrophotometric methods or in competition experiments with paraoxon. Increases or decreases in the steric bulk of the retained groups generally reduced the rate of hydrolysis, while modifications of the leaving group modulated both binding and turnover. Studies on the hydrolysis of phosphoryl azide analogs as well as amino‐modified paraoxon analogs, the former being developed as photoaffinity labels, found enhanced tolerance of structural modifications when compared with O‐alkyl‐substituted molecules. Results from computational modeling predict a predominant active site binding mode for these molecules, which is consistent with several proposed catalytic mechanisms in the literature and from which a molecular‐level explanation of the experimental trends is attempted. Overall, the results of this study suggest that while paraoxonase‐1 is a promiscuous enzyme, there are substantial constraints in the active site pocket, which may relate to both the leaving group and the retained portion of paraoxon analogs. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
684.
685.
In the present investigation hepatitis B surface antigen (HBsAg) encapsulated liposomes were developed and coupled with Ulex europaeus agglutinin 1 (UEA-1) to increase transmucosal uptake by M-cells of the Peyer's patches. The liposomes were characterized for shape, size, polydispersity and encapsulation efficiency. Bovine submaxillary mucin (BSM) was used as a biological model for the in vitro determination of lectin activity and specificity. Dual staining technique was used to investigate targeting of lectinized liposomes to the M-cells. Anti-HBsAg IgG response in serum and anti-HBsAg sIgA level in various mucosal fluids was estimated by using ELISA, following oral immunization with lectinized and non-lectinized liposomes in Balb/c mice. Additionally, interleukin-2 (IL-2) and interferon-γ (IFN-γ) level in the spleen homogenates was determined. The results suggest that lectinized liposomes were successfully developed, exhibited increased activity with BSM as compared to non-lectinized liposomes and α-l-fucose specificity of the lectinized liposomes was also maintained. The lectinized liposomes were predominantly targeted to the M-cells. The serum anti-HBsAg IgG titre obtained after 3 consecutive days oral immunizations with HBsAg encapsulated lectinized liposomes and boosting after third week was comparable with the titre recorded after single intramuscular prime and third week boosting with alum-HBsAg. Moreover, lectinized liposomes induced higher sIgA level in mucosal secretions and cytokines level in the spleen homogenates. The results showed that the developed surface modified liposomes could be a potential module for the development of effective mucosal vaccines. 相似文献
686.
687.
Raul Quijada Jairton Dupont Dione Corrêa Silveira Mrcia S. Lacerda Miranda Rosngela B. Scipioni 《Macromolecular rapid communications》1995,16(5):357-362
This work reports a comparative study of the catalytic behaviour for a series of metallocenes derived from Ti, Zr, Hf and Nb, which after activation with methylaluminoxane can polymerize ethylene. Results show that the Zr metallocene with a (CH3)2Si Bridge presents the highest activity, and the metallocenes based on Hf and Nb do not show any significant activity under the tested conditions. 相似文献
688.
Since 1961, aliphatic polyisocyanates based on HDI-biurets are used as light stable hardeners for 2-K polyurethane coatings. The market introduction of the HDI-isocyanurates or simply 'trimers' in the early 1980's was driven by their lower viscosity and their better monomer stability. The most recent development in HDI-polyisocyanate research are the iminooxadiazinediones (asymmetric trimers). In this paper, a new product based on that technology with a very low viscosity (700 mPas@23°C) and a NCO-functionality of more than 3 is presented. Because of its low viscosity, this hardener can be easily incorporated into aqueous systems and is the solution for high and full solids coatings as well. 相似文献
689.
690.
Thermoluminescene (TL) of synthetic quartz specimens under different physical conditions is investigated. An analysis for one of the prominent glow peaks has been done using the peak shape method. Further, on the basis of extracted trap level spectroscopic information, the results are explained. It is found that with different physical conditions characteristics of trapping level changes systematically. 相似文献