全文获取类型
收费全文 | 2134篇 |
免费 | 508篇 |
国内免费 | 187篇 |
专业分类
化学 | 910篇 |
晶体学 | 12篇 |
力学 | 176篇 |
综合类 | 47篇 |
数学 | 508篇 |
物理学 | 1176篇 |
出版年
2024年 | 3篇 |
2023年 | 22篇 |
2022年 | 54篇 |
2021年 | 74篇 |
2020年 | 73篇 |
2019年 | 67篇 |
2018年 | 57篇 |
2017年 | 79篇 |
2016年 | 98篇 |
2015年 | 113篇 |
2014年 | 169篇 |
2013年 | 146篇 |
2012年 | 140篇 |
2011年 | 135篇 |
2010年 | 109篇 |
2009年 | 125篇 |
2008年 | 167篇 |
2007年 | 131篇 |
2006年 | 156篇 |
2005年 | 121篇 |
2004年 | 123篇 |
2003年 | 95篇 |
2002年 | 83篇 |
2001年 | 81篇 |
2000年 | 77篇 |
1999年 | 47篇 |
1998年 | 43篇 |
1997年 | 38篇 |
1996年 | 37篇 |
1995年 | 27篇 |
1994年 | 23篇 |
1993年 | 17篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 11篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有2829条查询结果,搜索用时 31 毫秒
101.
Dynamic and Quantitative Control of the DNA‐Mediated Growth of Gold Plasmonic Nanostructures
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Jianlei Shen Lifeng Xu Dr. Chunpeng Wang Dr. Hao Pei Prof.Dr. Renzhong Tai Prof.Dr. Shiping Song Prof.Dr. Qing Huang Prof.Dr. Chunhai Fan Prof.Dr. Gang Chen 《Angewandte Chemie (International ed. in English)》2014,53(32):8338-8342
Reproducible and controllable growth of nanostructures with well‐defined physical and chemical properties is a longstanding problem in nanoscience. A key step to address this issue is to understand their underlying growth mechanism, which is often entangled in the complexity of growth environments and obscured by rapid reaction speeds. Herein, we demonstrate that the evolution of size, surface morphology, and the optical properties of gold plasmonic nanostructures could be quantitatively intercepted by dynamic and stoichiometric control of the DNA‐mediated growth. By combining synchrotron‐based small‐angle X‐ray scattering (SAXS) with transmission electron microscopy (TEM), we reliably obtained quantitative structural parameters for these fine nanostructures that correlate well with their optical properties as identified by UV/Vis absorption and dark‐field scattering spectroscopy. Through this comprehensive study, we report a growth mechanism for gold plasmonic nanostructures, and the first semiquantitative revelation of the remarkable interplay between their morphology and unique plasmonic properties. 相似文献
102.
Julie Andrez Dr. Jacques Pécaut Pierre‐Alain Bayle Dr. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2014,53(39):10448-10452
The synthesis, structure, and reactivity of stable homoleptic heterometallic LnL4K2 complexes of divalent lanthanide ions with electron‐rich tris(tert‐butoxy)siloxide ligands are reported. The [Ln(OSi(OtBu)3)4K2] complexes (Ln=Eu, Yb) are stable at room temperature, but they promote the reduction of azobenzene to yield the KPhNNPh radical anion as well as the reductive cleavage of CS2 to yield CS32? as the major product. The EuIII complex of the radical anion PhNNPh is structurally characterized. Moreover, [Yb(OSi(OtBu)3)4K2] can reduce CO2 at room temperature. Release of the reduction products in D2O shows the quantitative formation of both oxalate and carbonate in a 1:2.2 ratio. The bulky siloxide ligands enforce the labile binding of the reduction products providing the opportunity to establish a closed synthetic cycle for the YbII‐mediated CO2 reduction. These studies show that the presence of four electron‐rich siloxide ligands renders their EuII and YbII complexes highly reactive. 相似文献
103.
Discovery of Cell‐Permeable Inhibitors That Target the BRCT Domain of BRCA1 Protein by Using a Small‐Molecule Microarray
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhenkun Na Sijun Pan Dr. Mahesh Uttamchandani Prof. Dr. Shao Q. Yao 《Angewandte Chemie (International ed. in English)》2014,53(32):8421-8426
BRCTs are phosphoserine‐binding domains found in proteins involved in DNA repair, DNA damage response and cell cycle regulation. BRCA1 is a BRCT domain‐containing, tumor‐suppressing protein expressed in the cells of breast and other human tissues. Mutations in BRCA1 have been found in ca. 50 % of hereditary breast cancers. Cell‐permeable, small‐molecule BRCA1 inhibitors are promising anticancer agents, but are not available currently. Herein, with the assist of microarray‐based platforms, we have discovered the first cell‐permeable protein–protein interaction (PPI) inhibitors against BRCA1. By targeting the (BRCT)2 domain, we showed compound 15 a and its prodrug 15 b inhibited BRCA1 activities in tumor cells, sensitized these cells to ionizing radiation‐induced apoptosis, and showed synergistic inhibitory effect when used in combination with Olaparib (a small‐molecule inhibitor of poly‐ADP‐ribose polymerase) and Etoposide (a small‐molecule inhibitor of topoisomerase II). Unlike previously reported peptide‐based PPI inhibitors of BRCA1, our compounds are small‐molecule‐like and could be directly administered to tumor cells, thus making them useful for future studies of BRCA1/PARP‐related pathways in DNA damage and repair response, and in cancer therapy. 相似文献
104.
Jun‐Jie Shen Prof. Shou‐Fei Zhu Dr. Yan Cai Huan Xu Xiu‐Lan Xie Prof. Qi‐Lin Zhou 《Angewandte Chemie (International ed. in English)》2014,53(48):13188-13191
An iron‐catalyzed asymmetric intramolecular cyclopropanation was realized in high yields and excellent enantioselectivity (up to 97 % ee) by using the iron complexes of chiral spiro‐bisoxazoline ligands as catalysts. The superiority of iron catalysts exhibited in this reaction demonstrated the potential abilities of this sustainable metal in asymmetric carbenoid transformation reactions. 相似文献
105.
Rhodium(III)‐Catalyzed Transannulation of Cyclopropenes with N‐Phenoxyacetamides through CH Activation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hang Zhang Kang Wang Bo Wang Heng Yi Fangdong Hu Dr. Changkun Li Dr. Yan Zhang Prof. Dr. Jianbo Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13234-13238
An efficient rhodium(III)‐catalyzed synthesis of 2H‐chromene from N‐phenoxyacetamides and cyclopropenes has been developed. The reaction represents the first example of using cyclopropenes as a three‐carbon unit in rhodium(III)‐catalyzed C(sp2)? H activations. 相似文献
106.
Masaki Kondo Junichiro Kanazawa Tomohiro Ichikawa Takumi Shimokawa Yuki Nagashima Kazunori Miyamoto Masanobu Uchiyama 《Angewandte Chemie (International ed. in English)》2020,59(5):1970-1974
The silaboration of [1.1.1]propellane enables direct introduction of B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive‐free conditions. The silaborated BCP can be obtained on a gram‐scale in a single step without the need for column‐chromatographic purification, and is storable and easy to handle, providing a versatile synthetic intermediate for BCP derivatives. We also describe various conversions of the C?B/C?Si bonds on the BCP scaffold, including development of a modified Suzuki–Miyaura cross‐coupling reaction at the highly sterically hindered bridgehead sp3 carbon center of the BCP skeleton using a combination of highly activated BCP boronic esters, copper(I) oxide, and a PdCl2(dppf) catalyst system. 相似文献
107.
Cem B. Yildiz Kinga I. Leszczyska Sandra Gonzlez‐Gallardo Michael Zimmer Akin Azizoglu Till Biskup Christopher W. M. Kay Volker Huch Henry S. Rzepa David Scheschkewitz 《Angewandte Chemie (International ed. in English)》2020,59(35):15087-15092
Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si3Tip4 (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR2CH2)(NtBu)2]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)2(NtBu)2Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate. 相似文献
108.
Denise D. Deppe Robert D. Miller John M. Torkelson 《Journal of Polymer Science.Polymer Physics》1996,34(17):2987-2997
A novel experimental approach involving fluorescence nonradiative energy transfer (NRET) is employed to study the Fickian diffusion of small molecules in rubbery poly(isobutyl methacrylate) (PiBMA) films near the glass transition, using a formalism that directly relates the small molecule translational diffusion coefficient, D, to changes in the normalized nonradiative energy transfer efficiency, EN. Values of D for pyrene, 1,3-bis-(1-pyrene) propane (BPP), 1,3-bis-(1-pyrene) decane (BPD), 9,10-bis-phenyl ethynyl anthracene (BPEA), diphenyl Disperse Red 4 (DPDR4), and decacyclene in PiBMA are measured over temperatures ranging from approximately Tg to Tg + 25°C. Among these chromophores, significant differences in both the magnitude and temperature dependence of D are observed which are attributed to differences in molecule shape and flexibility, as well as molar volume. Other factors being equal, chromophore flexibility was shown both to increase the magnitude of D and to decrease its dependence on temperature, as does an increase in aspect ratio. For BPD, these effects are attributed to the ability of the flexible molecule to diffuse in a piecewise manner, requiring the cooperative mobility of fewer polymer chain segments than a rigid molecule of the same molar volume. For BPEA and DPDR4, this deviation from D being dominated by molar volume effects is attributed the to high aspect ratio of these elongated molecules. © 1996 John Wiley & Sons, Inc. 相似文献
109.
平面波经小圆孔非傍轴衍射的轴上光强解析分析 总被引:3,自引:2,他引:1
用亥姆霍兹 基尔霍夫积分定理和基尔霍夫边界条件,推导出了平面波经小圆孔非傍轴衍射时轴上强度的简单解析表达式,研究了平面波经小圆孔后整个衍射空间非傍轴的轴上光强分布.给出了计算圆孔菲涅尔数的精确公式,重新检查了通常的菲涅尔数公式的有效性.数值计算显示,应用解析表达式所得的结果与应用衍射积分公式所得的结果完全一致. 相似文献
110.