全文获取类型
收费全文 | 43372篇 |
免费 | 128篇 |
国内免费 | 163篇 |
专业分类
化学 | 33785篇 |
晶体学 | 6篇 |
力学 | 89篇 |
综合类 | 4篇 |
数学 | 85篇 |
物理学 | 9694篇 |
出版年
2022年 | 12篇 |
2021年 | 6篇 |
2020年 | 8篇 |
2019年 | 8篇 |
2018年 | 16篇 |
2017年 | 10篇 |
2016年 | 18篇 |
2015年 | 12篇 |
2014年 | 19篇 |
2013年 | 20篇 |
2012年 | 5008篇 |
2011年 | 7096篇 |
2010年 | 1030篇 |
2009年 | 176篇 |
2008年 | 4482篇 |
2007年 | 4459篇 |
2006年 | 4475篇 |
2005年 | 4091篇 |
2004年 | 2956篇 |
2003年 | 2141篇 |
2002年 | 1794篇 |
2001年 | 1021篇 |
2000年 | 1229篇 |
1999年 | 278篇 |
1998年 | 107篇 |
1997年 | 106篇 |
1996年 | 405篇 |
1995年 | 266篇 |
1994年 | 387篇 |
1993年 | 590篇 |
1992年 | 481篇 |
1991年 | 161篇 |
1990年 | 159篇 |
1989年 | 127篇 |
1988年 | 89篇 |
1987年 | 88篇 |
1986年 | 118篇 |
1985年 | 71篇 |
1984年 | 10篇 |
1983年 | 14篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1972年 | 15篇 |
1958年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
Hua-Hua Wang Yi-Yu Jiang Mian HR Mahmood Hai-Yang Liu Herman H.Y. Sung Ian D. Williams Chi K. Chang 《中国化学快报》2015,26(5):529-533
Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ). 相似文献
2.
催化裂化条件下噻吩与改性Y分子筛的作用机制 《燃料化学学报》2015,43(7):862-869
以HY、NiY和稀土离子改性的Y分子筛(REY)为研究对象,采用固定床装置评价噻吩模拟油催化裂化性能;运用气相色谱-氢火焰离子发光检测器(GC-FID)、气相色谱-硫化学发光检测器(GC-SCD)和原位红外光谱技术分析产物,关联分子筛的酸性,研究催化裂化条件下噻吩与改性Y分子筛的作用机制。实验结果表明,催化裂化条件下,噻吩与分子筛的作用机制差异主要取决于与B酸或L酸相关的非骨架铝物种或金属离子物种的存在形式。其中,NiY分子筛中,噻吩主要是吸附在与NiOH+物种相关的L酸中心,而Ni4AlO43+等物种减弱B酸性中心从而降低其裂化性能。对HY来说,噻吩易在与AlO+等物种相邻的B酸中心上聚合形成三联噻吩,并发生一定的氢转移和裂化反应;而对REY而言,分子筛中与RE物种相关的L酸位会促进噻吩在与非骨架铝羟基等物种(如Al(OH)2+、Al(OH)2+等)相邻的B酸中心形成的二联噻吩发生氢转移和裂化反应。 相似文献
3.
Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical perspectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and structural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science. 相似文献
4.
Y修饰CuO/ZrO催化剂高效催化水煤气变换反应制氢 《燃料化学学报》2017,45(9):1137-1145
采用水热法制备了具有不同Y掺杂量的单分散ZrO_2纳米粒子(n(Y)/n(Y+Zr)=0-5%),并以其为载体采用沉积-沉淀法制得CuO/ZrO_2催化剂;考察了富氢气氛下上述催化剂的水煤气变换反应(WGS)催化性能。结果表明,掺杂Y后催化剂的活性明显提高,其中,载体掺杂2%Y的催化剂具有最佳的催化活性,在270℃时的CO转化率高达91.4%,明显高于研究较多的CuO/ZnO和CuO/CeO_2催化剂。X射线粉末衍射、N_2物理吸附-脱附、N_2O滴定、扫描电镜和CO程序升温还原等表征结果表明,Y~(3+)掺入了ZrO_2的晶格并对催化剂的结构和还原性能产生直接影响。Y助剂的引入一方面促进了CuO在ZrO_2表面的分散,提高了催化剂表面活性Cu-[O]-Zr物种的含量;另一方面,改善了催化剂的颗粒单分散性和织构性能。载体掺杂2%Y助剂的样品具有较高的Cu-[O]-Zr物种含量、较佳的颗粒单分散性和织构性能,且其表面的Cu-[O]-Zr物种和活性羟基具有较佳的还原性能,因而表现出较高的催化活性 相似文献
5.
改性Y型分子筛对硫醇硫醚的吸附脱除研究 《燃料化学学报》2017,45(12):1467-1472
通过液相离子交换法制备了Cu(I)Y、Ni Y、Ce Y分子筛,以XRD、低温N2吸附-脱附、NH3-TPD、吡啶红外Py-FTIR等方法对其进行物性表征。利用固定床技术、WK-2D微库伦仪及硫化学发光检测GC-SCD色谱评价了改性分子筛对于硫含量300μg/g模拟油(含硫化合物二丙硫醚、环己硫醇和1-庚硫醇与壬烷配制)及HDS汽油的吸附脱硫性能。结果表明,吸附剂对模拟油和HDS燃料油品中硫醇硫醚具有吸附效果,且改性后的分子筛在吸附脱硫过程中,强的B酸对于吸附脱硫有负作用,会使油品中硫醇硫醚发生催化反应,聚合的大分子硫化物遮盖及阻塞吸附活性位点,从而使吸附剂不能够完全地吸附硫化物,造成吸附硫容较小,而弱L酸无催化活性对吸附脱硫有正面影响。 相似文献
6.
应用相位移法的二维光栅测量 总被引:4,自引:0,他引:4
本文介绍了二种二维位移测量的光栅方法。测试系统采用CCD摄象系统记录正交光栅图象,通过调整摄象机变焦镜头的放大倍数来控制采样的空间频率。采样后用数字信号处理的方法,通过软件手段实现水平向和垂直向光栅信号的分离,然后运用了相位移技术及载波—相位移技术得到二维位移。所开发的测试系统除具有高精度、高灵敏度的特点外,还具有较高的空间分辨率。 相似文献
7.
Chon KH Zhong Y Wang H Ju K Jan KM 《Nonlinear dynamics, psychology, and life sciences》2006,10(2):163-185
This work introduces a modified Principal Dynamic Modes (PDM) methodology using eigenvalue/eigenvector analysis to separate individual components of the sympathetic and parasympathetic nervous contributions to heart rate variability. We have modified the PDM technique to be used with even a single output signal of heart rate variability data, whereas the original PDMs required both input and output data. This method specifically accounts for the inherent nonlinear dynamics of heart rate control, which the current method of power spectrum density (PSD) is unable to do. Propranolol and atropine were administered to normal human volunteers intravenously to inhibit the sympathetic and parasympathetic activities, respectively. With separate applications of the respective drugs, we found a significant decrease in the amplitude of the waveforms that correspond to each nervous activity. Furthermore, we observed near complete elimination of these dynamics when both drugs were given to the subjects. Comparison of our method to the conventional low/high frequency ratio of PSD shows that PDM methodology provides much more accurate assessment of the autonomic nervous balance by separation of individual components of the autonomic nervous activities. The PDM methodology is expected to have an added benefit that diagnosis and prognostication of a patient's health can be determined simply via a non-invasive electrocardiogram. 相似文献
8.
A simple and efficient synthesis of highly substituted pyrroles was achieved in water medium via multi-component strategy, using amine,DMAD/DEAD as well as phenacyl bromide catalyzed by β-CD.Utilizing this protocol various pyrrole derivatives were synthesized in good to excellent yields. 相似文献
9.
T Abe K Horiuchi H Kikuchi T Aritsuka Y Takata E Fukushi Y Fukushi J Kawabata K Ueno S Onodera N Shiomi 《Chemistry Central journal》2012,6(1):89
ABSTRACT: BACKGROUND: Sugar beet molasses is a viscous by-product of the processing of sugar beets into sugar. The molasses is known to contain sucrose and raffinose, a typical trisaccharide, with a well-established structure. Although sugar beet molasses contains various other oligosaccharides as well, the structures of those oligosaccharides have not been examined in detail. The purpose of this study was isolation and structural confirmation of these other oligosaccharides found in sugar beet molasses. RESULTS: Four oligosaccharides were newly isolated from sugar beet molasses using high-performance liquid chromatography (HPLC) and carbon-Celite column chromatography. Structural confirmation of the saccharides was provided by methylation analysis, matrix-assisted laser desorption/ionaization time of flight mass spectrometry (MALDI-TOF-MS), and nuclear magnetic resonance (NMR) measurements. CONCLUSION: The following oligosaccharides were identified in sugar beet molasses: beta-D-galactopyranosyl-(1- > 6)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named beta-planteose), alpha-D-galactopyranosyl-(1- > 1)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named1-planteose), alpha-D-glucopyranosyl-(1- > 6)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (theanderose), and beta-D-glucopyranosyl-(1- > 3)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (laminaribiofructose). 1-planteose and laminaribiofructose were isolated from natural sources for the first time. 相似文献
10.
K Nilson J Åhlund MN Shariati J Schiessling P Palmgren B Brena E Göthelid F Hennies Y Huismans F Evangelista P Rudolf M Göthelid N Mårtensson C Puglia 《The Journal of chemical physics》2012,137(4):044708
X-ray spectroscopy studies of potassium intercalated metal-free phthalocyanine multilayers adsorbed on Al(110) have been undertaken. Photoelectron spectroscopy measurements show the presence of several charge states of the molecules upon K intercalation, due to a charge transfer from the alkali. In addition, the comparison of valence band photoemission spectra with the density functional theory calculations of the density of states of the H(2)Pc(-) anion indicates a filling of the formerly lowest unoccupied molecular orbital by charge transfer from the alkali. This is further confirmed by x-ray absorption spectroscopy (XAS) studies, which show a decreased density of unoccupied states. XAS measurements in different experimental geometries reveal that the molecules in the pristine film are standing upright on the surface or are only slightly tilted away from the surface normal but upon K intercalation, the molecular orientation is changed in that the tilt angle of the molecules increases. 相似文献