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   5925篇
  免费   315篇
  国内免费   57篇
化学   4311篇
晶体学   26篇
力学   101篇
综合类   1篇
数学   959篇
物理学   899篇
  2023年   50篇
  2022年   81篇
  2021年   111篇
  2020年   151篇
  2019年   128篇
  2018年   105篇
  2017年   89篇
  2016年   185篇
  2015年   159篇
  2014年   206篇
  2013年   286篇
  2012年   464篇
  2011年   491篇
  2010年   233篇
  2009年   180篇
  2008年   403篇
  2007年   391篇
  2006年   392篇
  2005年   357篇
  2004年   326篇
  2003年   240篇
  2002年   212篇
  2001年   90篇
  2000年   51篇
  1999年   42篇
  1998年   42篇
  1997年   51篇
  1996年   52篇
  1995年   45篇
  1994年   58篇
  1993年   55篇
  1992年   54篇
  1991年   49篇
  1990年   34篇
  1989年   29篇
  1988年   26篇
  1987年   25篇
  1986年   29篇
  1985年   30篇
  1984年   17篇
  1983年   25篇
  1982年   25篇
  1981年   24篇
  1980年   21篇
  1979年   28篇
  1978年   14篇
  1976年   14篇
  1975年   22篇
  1974年   16篇
  1973年   22篇
排序方式: 共有6297条查询结果,搜索用时 312 毫秒
51.
Sensitization on skin exposed to acute low-dose UVB irradiation separates normal humans into two phenotypically distinct groups: One group, following sensitization on UVB-irradiated skin, develops contact sensitivity, designated UVB resistant (UVB-R) and the second group, following sensitization on UVB-irradiated skin, fails to develop contact sensitivity, designated UVB susceptible (UVB-S). To investigate whether UVB susceptibility in humans is related to antigen-presenting activity in the skin we studied the effect of UVB irradiation on the number and function of the epidermal antigen-presenting cells in volunteers identified as UVB-R and UVB-S. Single cell suspensions of epidermal cells from control skin and skin exposed to 3 minimal erythema doses (MED) of UVB 3 days previously were stained for Langerhans cells (CD1a+HLA-DR+) and epidermal macrophages (CD1a-HLA-DR+). The UVB exposure of the skin significantly decreased the percentage of Langerhans cells (UVB-R: n = 7, P < 0.02, UVB-S: n = 6, P < 0.03) and increased the percentage of epidermal macrophages (UVB-R: n = 7, P < 0.03, UVB-S: n = 6, P < 0.03) however to the same degree in both the UVBR and the UVB-S group. To study the effect on Langerhans cell alloreactivity, epidermal cells were harvested immediately after UVB irradiation. However, in both UVB-R and UVB-S subjects the Langerhans cell alloreactivity was blocked to the same degree immediately after UVB irradiation compared to nonirradiated epidermal cells. To determine the effect of UVB irradiation on epidermal macrophages, epidermal cells were harvested 3 days after UVB irradiation. Irradiated epidermal cells from both UVB-R and UVB-S subjects demonstrated a strong antigen-presenting capacity compared to epidermal cells from control skin leading to activation of T cells that mainly secrete interferon (1FN)-γ and not interleukin (IL)-4. In conclusion we found that UVB susceptibility was not correlated with the number of Langerhans cells or epidermal macrophages in the skin at the same time of sensitization. Neither was it correlated with the capacity of Langerhans cells nor UVB-induced epidermal macrophages to activate T cells in vitro.  相似文献   
52.
Highly-functionalised difluorinated cyclooctenones were synthesised from trifluoroethanol using either metallated difluoroenol acetal or carbamate chemistry, followed by a [2,3]-Wittig rearrangement or aldol reaction. Efficient RCM reactions afforded the title compounds which showed rather restricted fluxional behaviour by VT (19)F NMR. Topological characterisation by molecular modelling and NOESY/ROESY experiments offered a number of challenges, but allowed the identification of two favoured boat-chair conformers which interconverted by pseudorotation with relatively large activation barriers.  相似文献   
53.
The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed.  相似文献   
54.
Porphyrins have been widely used in the self‐assembly of metallo‐supramolecules. In this study, we introduced 2,2':6,2"‐terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self‐assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI‐MS and traveling‐wave ion mobility‐mass spectrometry (TWIM‐MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.  相似文献   
55.
ULTRAVIOLET SOLAR RADIATION IN THE HIGH LATITUDES OF SOUTH AMERICA   总被引:6,自引:0,他引:6  
Abstract Measurements of the UV solar irradiance are available from Ushuaia, Tierra del Fuego during the spring and summer seasons of 4 consecutive years beginning in 1989. In addition, column ozone amounts derived from satellite-based measurements exist for this location over the entire period from 1980 through 1991. Monthly mean column ozone over Ushuaia shows a general decline over the observing period, and a large day-to-day variability exists within a given month. Ozone amounts for the years 1980 through 1986 combined with a model of radiative transfer provide a climatological baseline against which to interpret the more recent ground-based irradiance data. We focus on monthly mean noontime irradiances integrated over 5 nm wide spectral bands near 305 nm and 340 nm, respectively. Measurements in the 340 nm band show that cloudiness has a large influence on both the absolute monthly mean irradiances and their interannual variability. For example, during December the 340 nm band irradiance varied from approximately 50% of the clear-sky value in 1992 to 65% in 1991. When the influence of cloudiness is removed, most of the months show irradiances in the 305 nm band that are larger than predicted from the climatological ozone amounts. The largest percentage enhancement occurred in October 1991 when the irradiance exceeded the baseline by 56%. The largest absolute irradiances occur in December, where the measurements range from 5.8% below the baseline in 1991 to 31% above in 1990.  相似文献   
56.
Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species.  相似文献   
57.
The onset of pressure-induced hydration and volume expansion is lowered to 0.6 GPa via the increased flexibility of the host lattice using isomorphous substitution of Al by larger Ga in a sodium aluminosilicate natrolite.  相似文献   
58.
The dinuclear iron(II) complex [(pypzH)(NCSe)Fe([micro sign]-pypz)(2)Fe(NCSe)(pypzH)].2H(2)O displays a single, sharp spin crossover transition between the [HS-HS] and [LS-LS] states and is structurally characterised above and below the T(1/2)= 225 K value  相似文献   
59.
NMR spectroscopy and X-ray crystallography, the two primary experimental methods for protein structure determination at high resolution, have different advantages and disadvantages in terms of sample preparation and data collection and analysis. It is therefore of interest to assess their complementarity when applied to small proteins. Structural genomics/proteomics projects provide an ideal opportunity to make such comparisons as they generate data in a systematic manner for large enough numbers of proteins to allow firm conclusions to be drawn. Here we report a comparison for 263 unique proteins screened by both NMR spectroscopy and X-ray crystallography in our structural proteomics pipeline. Only 21 targets (8%) were deemed amenable to both methods based on an initial 2D 15N-HSQC NMR spectrum and optimized crystallization trials. However, the use of both methods in the pipeline increased the total number of targets amenable to structure determination to 107, with 43 amenable to NMR only and 43 amenable to X-ray crystallographic methods only. We did not observe a correlation between 15N-HSQC spectral quality and the success of the same protein in crystallization screens. Similar results were found for an independent set of 159 proteins as reported in the accompanying paper by Snyder et al. Thus, we conclude that both methods are highly complementary, and in order to increase the number of proteins suited for structure determination, we suggest that both methods be used in parallel in screening of all small proteins for structure determination.  相似文献   
60.
Helical polymers appended with paired structurally different enantiomers, which have opposing helical sense preferences, yield a new kind of relationship between optical activity and temperature, and also reveal unusual details of the nature of chiral interactions. Consistent with a statistical physical theory developed for these experiments, the proportion of the competing chiral groups, determined by synthesis, fixes the compensation temperature at which the helical senses are equally populated. The lyotropic liquid crystal state formed by these polymers yields therefore a nematic state at any chosen temperature over a very wide range, with a cholesteric state arising with tightening pitch as temperature deviates from this point. Far from the nematic temperature, the pitch reaches the nanometer scale and therefore the reflection of visible light. Before crossing zero at the nematic temperature, the optical activity becomes so large that it may be observed with the unaided eye through crossed polarizers.  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