全文获取类型
收费全文 | 1655篇 |
免费 | 42篇 |
国内免费 | 13篇 |
专业分类
化学 | 1156篇 |
晶体学 | 26篇 |
力学 | 34篇 |
数学 | 247篇 |
物理学 | 247篇 |
出版年
2022年 | 11篇 |
2021年 | 17篇 |
2020年 | 24篇 |
2019年 | 17篇 |
2018年 | 19篇 |
2017年 | 23篇 |
2016年 | 23篇 |
2015年 | 24篇 |
2014年 | 33篇 |
2013年 | 102篇 |
2012年 | 118篇 |
2011年 | 92篇 |
2010年 | 63篇 |
2009年 | 33篇 |
2008年 | 85篇 |
2007年 | 104篇 |
2006年 | 96篇 |
2005年 | 83篇 |
2004年 | 89篇 |
2003年 | 70篇 |
2002年 | 68篇 |
2001年 | 22篇 |
2000年 | 21篇 |
1999年 | 18篇 |
1998年 | 13篇 |
1997年 | 15篇 |
1996年 | 23篇 |
1995年 | 22篇 |
1994年 | 20篇 |
1993年 | 14篇 |
1992年 | 23篇 |
1991年 | 21篇 |
1990年 | 17篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 15篇 |
1984年 | 16篇 |
1983年 | 10篇 |
1982年 | 12篇 |
1981年 | 16篇 |
1980年 | 13篇 |
1979年 | 12篇 |
1978年 | 16篇 |
1977年 | 11篇 |
1976年 | 18篇 |
1975年 | 14篇 |
1974年 | 10篇 |
1973年 | 13篇 |
1970年 | 11篇 |
排序方式: 共有1710条查询结果,搜索用时 31 毫秒
81.
Bobo Dang Dr. Tomoya Kubota Prof. Dr. Ana M. Correa Prof. Dr. Francisco Bezanilla Prof. Dr. Stephen B. H. Kent 《Angewandte Chemie (International ed. in English)》2014,53(34):8970-8974
Ts1 toxin is a protein found in the venom of the Brazilian scorpion Tityus serrulatus. Ts1 binds to the domain II voltage sensor in the voltage‐gated sodium channel Nav and modifies its voltage dependence. In the work reported here, we established an efficient total chemical synthesis of the Ts1 protein using modern chemical ligation methods and demonstrated that it was fully active in modifying the voltage dependence of the rat skeletal muscle voltage‐gated sodium channel rNav1.4 expressed in oocytes. Total synthesis combined with click chemistry was used to label the Ts1 protein molecule with the fluorescent dyes Alexa‐Fluor 488 and Bodipy. Dye‐labeled Ts1 proteins retained their optical properties and bound to and modified the voltage dependence of the sodium channel Nav. Because of the highly specific binding of Ts1 toxin to Nav, successful chemical synthesis and labeling of Ts1 toxin provides an important tool for biophysical studies, histochemical studies, and opto‐pharmacological studies of the Nav protein. 相似文献
82.
Stereocontrolled Synthesis of 1,5‐Stereogenic Centers through Three‐Carbon Homologation of Boronic Esters
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)
Phillip J. Unsworth Dr. Daniele Leonori Prof. Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2014,53(37):9846-9850
Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a PdII‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon chains that bear 1,5‐stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)‐jasplakinolide. 相似文献
83.
Dr. Abshar Hasan Dr. Kyueui Lee Dr. Kunal Tewari Prof. Lalit M. Pandey Prof. Phillip B. Messersmith Prof. Karen Faulds Dr. Michelle Maclean Dr. King Hang Aaron Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5789-5793
Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N-substituted glycine) „peptoids“ are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMP-mimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification strategy for enabling alkyne–azide „click“ coupling on amino-functionalized surfaces. Our results verified that the N- and C-terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a „volumetric“ spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti-biofouling. 相似文献
84.
Brylee David B. Tiu Peyman Delparastan Max R. Ney Matthias Gerst Phillip B. Messersmith 《Angewandte Chemie (International ed. in English)》2020,59(38):16616-16624
The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino‐catechol synergy, polymeric pressure‐sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel‐inspired lysine‐ and aromatic‐rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM‐assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance. 相似文献
85.
86.
Zhixian Zhou Hongna Han Tiesheng Li Yanjun Xing Yangjie Wu Xian Xin Zhang Reed M. Izatt N. Kent Dalley Jerald S. Bradshaw Weijie Chai Cunheng He 《Structural chemistry》1999,10(3):177-185
Reactions of CsI and HgI2 with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)2]2[Hg2I6] (1) and {[Cs(15C5)]2[Hg2I6]}n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs+ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5)
2
+
cations and a Hg2I
6
2-
anion. Cs+ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5)
2
+
and anionic Hg2I
6
2-
are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]2[Hg2I6] units. Each structural unit contains two Cs(15C5)+ cations and a Hg2I
6
2-
anion. Cs+ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg2I
6
2-
, and an iodine atom of Hg2I
6
2-
in an adjacent structural unit. The interactions between the Cs+ of Cs(15C5)+ and an I– in Hg2I
6
2-
from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg2I
6
2-
in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P21/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) Å, = 111.0(1)°, V = 3860 Å3, Z = 4, R = 0.082 (R
w = 0.089). Crystal data for 2: space group P21/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) Å, = 91.54(3)°, V = 2146 Å3, Z = 4, R = 0.034 (R
w = 0.048). 相似文献
87.
Development and application of sub‐2‐μm particle CO2‐based chromatography coupled to mass spectrometry for comprehensive analysis of lipids in cottonseed extracts
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
88.
N. Kent Dalley Weiming Jiang Krzysztof E. Krakowiak Geng Wu D. Wade Walke Jerald S. Bradshaw Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(3):299-308
Hydrazino-crown ethers have been synthesized in only 3 or 4 steps starting from 1,2-diacetylhydrazine. The X-ray crystal structure of protonated hydrazino-19-crown-7 (2) showed that one of the hydrazino nitrogen atoms was directed outside the ring cavity. A solvent methanol molecule is held in the cavity of the host ligand by three hydrogen bonds involving two hydrogen atoms bonded to nitrogens of the ligand and the alcohol hydrogen of the methanol. The logK values for the interaction of2 with CH3NH
+
3
, Ag+, Pb2+, and Cd2+ were much less than those for the interaction of symmetrical triaza-l8-crown-6 (5) with the same cations. Hydrazino-crown2 reduced silver ions to silver metal when a solution of2 and silver ions in DMSO was allowed to stand for several days. 相似文献
89.
Wang J Struckmeier U Yang B Cool TA Osswald P Kohse-Höinghaus K Kasper T Hansen N Westmoreland PR 《The journal of physical chemistry. A》2008,112(39):9255-9265
This work provides experimental evidence on how the molecular compositions of fuel-rich low-pressure premixed flames are influenced as the oxygenates dimethyl ether (DME) or ethanol are incrementally blended into the propene fuel. Ten different flames with a carbon-to-oxygen ratio of 0.5, ranging from 100% propene (phi = 1.5) to 100% oxygenated fuel (phi = 2.0), are analyzed with flame-sampling molecular-beam mass spectrometry employing electron- or photoionization. Absolute mole fraction profiles for flame species with masses ranging from m/z = 2 (H2) to m/z = 80 (C6H8) are analyzed with particular emphasis on the formation of harmful emissions. Fuel-specific destruction pathways, likely to be initiated by hydrogen abstraction, appear to lead to benzene from propene combustion and to formaldehyde and acetaldehyde through DME and ethanol combustion, respectively. While the concentration of acetaldehyde increases 10-fold as propene is substituted by ethanol, it decreases as propene is replaced with DME. In contrast, the formaldehyde concentration rises only slightly with ethanol replacement but increases markedly with addition of DME. Allyl and propargyl radicals, the dominant precursors for benzene formation, are likely to be produced directly from propene decomposition or via allene and propyne. Benzene formation through propargyl radicals formed via unsaturated C2 intermediates in the decomposition of DME and ethanol is negligibly small. As a consequence, DME and ethanol addition lead to similar reductions of the benzene concentration. 相似文献
90.
研究了Er∶Yb∶YCa4O(BO3)3(简称Er∶Yb∶YCOB)的多晶制备和单晶生长,用提拉法生长出光学质量优良的Er∶Yb∶YCOB单晶,测量了其吸收光谱和荧光光谱,分析了其能级和泵浦原理,并进行了以激光二极管为抽运源的激光试验,实现了Er∶Yb∶YCOB晶体的在1.55μm附近110mW的激光输出,且斜效率达18.9;. 相似文献