首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2813篇
  免费   67篇
  国内免费   17篇
化学   1820篇
晶体学   27篇
力学   85篇
数学   469篇
物理学   496篇
  2021年   25篇
  2020年   40篇
  2019年   32篇
  2018年   27篇
  2017年   21篇
  2016年   45篇
  2015年   49篇
  2014年   46篇
  2013年   135篇
  2012年   137篇
  2011年   143篇
  2010年   83篇
  2009年   62篇
  2008年   162篇
  2007年   142篇
  2006年   167篇
  2005年   135篇
  2004年   101篇
  2003年   89篇
  2002年   96篇
  2001年   31篇
  2000年   24篇
  1999年   25篇
  1998年   32篇
  1997年   25篇
  1996年   25篇
  1995年   26篇
  1994年   30篇
  1993年   35篇
  1992年   29篇
  1991年   33篇
  1990年   28篇
  1989年   37篇
  1988年   29篇
  1987年   21篇
  1986年   21篇
  1985年   41篇
  1984年   47篇
  1983年   36篇
  1982年   47篇
  1981年   51篇
  1980年   31篇
  1979年   26篇
  1978年   38篇
  1977年   30篇
  1976年   48篇
  1975年   34篇
  1974年   34篇
  1973年   31篇
  1969年   18篇
排序方式: 共有2897条查询结果,搜索用时 19 毫秒
1.
To improve our understanding of the combustion characteristics of propyne, new experimental data for ignition delay times (IDTs), pyrolysis speciation profiles and flame speed measurements are presented in this study. IDTs for propyne ignition were obtained at equivalence ratios of 0.5, 1.0, and 2.0 in ‘air’ at pressures of 10 and 30 bar, over a wide range of temperatures (690–1460 K) using a rapid compression machine and a high-pressure shock tube. Moreover, experiments were performed in a single-pulse shock tube to study propyne pyrolysis at 2 bar pressure and in the temperature range 1000–1600 K. In addition, laminar flame speeds of propyne were studied at an unburned gas temperature of 373 K and at 1 and 2 bar for a range of equivalence ratios. A detailed chemical kinetic model is provided to describe the pyrolytic and combustion characteristics of propyne across this wide-ranging set of experimental data. This new mechanism shows significant improvements in the predictions for the IDTs, fuel pyrolysis and flame speeds for propyne compared to AramcoMech3.0. The improvement in fuel reactivity predictions in the new mechanism is due to the inclusion of the propyne + H?2 reaction system along with ?H radical addition to the triple bonds of propyne and subsequent reactions.  相似文献   
2.
Nonlinear Dynamics - The fluctuation of ions concentration across the cell membrane of neuron can generate a time varying electromagnetic field. Thus, memristors are used to realize the coupling...  相似文献   
3.
Spatiotemporal control over biochemical signaling processes involving G protein‐coupled receptors (GPCRs) is highly desired for dissecting their complex intracellular signaling. We developed sixteen photoswitchable ligands for the human histamine H3 receptor (hH3R). Upon illumination, key compound 65 decreases its affinity for the hH3R by 8.5‐fold and its potency in hH3R‐mediated Gi protein activation by over 20‐fold, with the trans and cis isomer both acting as full agonist. In real‐time two‐electrode voltage clamp experiments in Xenopus oocytes, 65 shows rapid light‐induced modulation of hH3R activity. Ligand 65 shows good binding selectivity amongst the histamine receptor subfamily and has good photolytic stability. In all, 65 (VUF15000) is the first photoswitchable GPCR agonist confirmed to be modulated through its affinity and potency upon photoswitching while maintaining its intrinsic activity, rendering it a new chemical biology tool for spatiotemporal control of GPCR activation.  相似文献   
4.
A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported, mediated by iridium(i) complexes supported by aminophenylphosphinite (NCOP) pincer ligands. The decarbonylation, which involves the cleavage of one C–C bond, one C–O bond, and two C–H bonds, along with formation of two new C–H bonds, was serendipitously discovered upon dehydrochlorination of an iridium(iii) complex containing an aza-18-crown-6 ether macrocycle. Intramolecular cleavage of macrocyclic and acyclic ethers was also found in analogous complexes featuring aza-15-crown-5 ether or bis(2-methoxyethyl)amino groups. Intermolecular decarbonylation of cyclic and linear ethers was observed when diethylaminophenylphosphinite iridium(i) dinitrogen or norbornene complexes were employed. Mechanistic studies reveal the nature of key intermediates along a pathway involving initial iridium(i)-mediated double C–H bond activation.

A unique chain-rupturing transformation that converts an ether functionality into two hydrocarbyl units and carbon monoxide is reported.  相似文献   
5.
Light‐driven molecular motors possess immense potential as central driving units for future nanotechnology. Integration into larger molecular setups and transduction of their mechanical motions represents the current frontier of research. Herein we report on an integrated molecular machine setup allowing the transmission of potential energy from a motor unit onto a remote receiving entity. The setup consists of a motor unit connected covalently to a distant and sterically encumbered biaryl receiver. By action of the motor unit, single‐bond rotation of the receiver is strongly accelerated and forced to proceed unidirectionally. The transmitted potential energy is directly measured as the extent to which energy degeneration is lifted in the thermal atropisomerization of this biaryl. Energy degeneracy is reduced by more than 1.5 kcal mol?1, and rate accelerations of several orders of magnitude in terms of the rate constants are achieved.  相似文献   
6.
Human skin is exposed to visible light (VL; 400–700 nm) and long-wavelength ultraviolet A1 (UVA1) radiation (370–400 nm) after the application of organic broad-spectrum sunscreens. The biologic effects of these wavelengths have been demonstrated; however, a dose–response has not been investigated. Ten subjects with Fitzpatrick skin phototype IV-VI were enrolled. Subjects were irradiated with 2 light sources (80–480 J cm−2): one comprising VL with less than 0.5% UVA1 (VL+UVA1) and the other pure VL. Skin responses were evaluated for 2 weeks using clinical and spectroscopic assessments. 4-mm punch biopsies were obtained from nonirradiated skin and sites irradiated with 480 J cm−2 of VL+UVA1 and pure VL 24 h after irradiation. Clinical and spectroscopic assessments demonstrated a robust response at VL+UVA1 sites compared with pure VL. Histology findings demonstrated a statistically significant increase in the marker of inflammation (P < 0.05) and proliferation (P < 0.05) at the irradiated sites compared with nonirradiated control. Threshold doses of VL+UVA1 resulting in biologic responses were calculated. Results indicate that approximately 2 h of sun exposure, which equates to VL+UVA1 dose (~400 J cm−2), is capable of inducing inflammation, immediate erythema and delayed tanning. These findings reinforce the need of photoprotection beyond the UV range.  相似文献   
7.
8.
9.
The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components.  相似文献   
10.
X-ray free-electron lasers produce brief flashes of X-rays that are of about a billion times higher peak brightness than achievable from storage ring sources. Such a tremendous jump in X-ray source capabilities, which came in 2009 when the Linac Coherent Light Source began operations, was unprecedented in the history of X-ray science. Protein structure determination through the method of macromolecular crystallography has consistently benefited from the many increases in source performance from rotating anodes to all generations of synchrotron facilities. But when confronted with the prospects of such bright beams for structural biology, enthusiastic proposals were tempered by trepidation of the effects of such beams on samples and challenges to record data [1 M. Wilmanns, J. Synchr. Rad. 7, 41 (2000).[Crossref], [PubMed] [Google Scholar]]. A decade after these discussions (and others in the USA) on the applications of X-ray FELs for biology, the first experiments took place at LCLS, giving results that fulfilled many of the dreams of the early visionaries. In particular, the concept that diffraction representing the pristine object could be recorded before the X-ray pulse completely vaporizes the object was validated [2 H.N. Chapman, Nature 470, 73 (2011).[Crossref], [PubMed], [Web of Science ®] [Google Scholar]], confirming predictions [3 R. Neutze, Nature 406, 753 (2000).[Crossref], [Web of Science ®] [Google Scholar]] that established dose limits could be vastly exceeded using femtosecond-duration pulses. The first experiments illuminated a path to achieve room-temperature structures free of radiation damage, from samples too small to provide useful data at synchrotron facilities, as well as providing the means to carry out time-resolved crystallography at femtoseconds to milliseconds. In the five years since, progress has been substantial and rapid, invigorating the field of macromolecular crystallography [4 J.C.H. Spence and H.N. Chapman, Phi. Trans. Roy. Soc. B 369, 20130309 (2014).[Crossref], [PubMed], [Web of Science ®] [Google Scholar], 5 I. Schlichting, IUCrJ 2, 246 (2015).[Crossref], [PubMed], [Web of Science ®] [Google Scholar]]. This phase of development is far from over, but with both the LCLS and the SPring-8 Ångström Compact Free-electron Laser (SACLA) providing facilities for measurements, the benefits of X-ray FELs are already being translated into new biological insights.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号