全文获取类型
收费全文 | 1664篇 |
免费 | 83篇 |
国内免费 | 5篇 |
专业分类
化学 | 1404篇 |
晶体学 | 17篇 |
力学 | 20篇 |
数学 | 72篇 |
物理学 | 239篇 |
出版年
2023年 | 16篇 |
2022年 | 26篇 |
2021年 | 33篇 |
2020年 | 37篇 |
2019年 | 35篇 |
2018年 | 38篇 |
2017年 | 21篇 |
2016年 | 56篇 |
2015年 | 46篇 |
2014年 | 72篇 |
2013年 | 91篇 |
2012年 | 119篇 |
2011年 | 174篇 |
2010年 | 83篇 |
2009年 | 76篇 |
2008年 | 113篇 |
2007年 | 89篇 |
2006年 | 85篇 |
2005年 | 71篇 |
2004年 | 79篇 |
2003年 | 63篇 |
2002年 | 51篇 |
2001年 | 26篇 |
2000年 | 17篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 13篇 |
1995年 | 8篇 |
1994年 | 12篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 5篇 |
1989年 | 9篇 |
1988年 | 11篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1969年 | 3篇 |
1968年 | 4篇 |
排序方式: 共有1752条查询结果,搜索用时 0 毫秒
101.
We herein report comparative analysis of two versions of the biosynthetic gene clusters of antimycins, a natural product family possessing up to 44 distinct entities. The biosynthetic pathway of antimycins is amenable to the high structural variation of the substrates, supported by successes in heterologous expression of the ant cluster and in fluorine incorporation. The latter facilitated the investigation of the structure-activity relationship into the usually invariable 3-formamidosalicylic acid moiety of the molecules. 相似文献
102.
Vendamme R Ohzono T Nakao A Shimomura M Kunitake T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2792-2799
Large-scale, self-supporting ultrathin films composed of an elastomeric polyacrylate network interpenetrated by a silica (SiO2) network were synthesized and characterized. The organic network was first photopolymerized and the silica structure was subsequently developed in situ in the preformed organic gel. Composition and morphology of the hybrid interpenetrated network (IPN) nanofilms were characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy and compared with the case of zirconia (ZrO2) hybrid IPN reported earlier. Young modulus, ultimate tensile strength, and ultimate tensile elongation were determined for different organic/inorganic molar ratios and give some insights on how the composition of the nanofilms influence their robustness and self-supporting properties. 相似文献
103.
The total synthesis of polygalolide A was accomplished through intramolecular C-glycosylation of glucal modified with siloxyfuran. The siloxyfuran group and siloxy substituent at the C-3 position played crucial roles in allowing direct access to the highly substituted oxabicyclo[3.2.1] core skeleton with correct quaternary stereogenic centers. 相似文献
104.
Dr. Ryu Yamasaki Dr. Masato Ohashi Kyotaro Maeda Takuya Kitamura Minami Nakagawa Korehito Kato Tetsushi Fujita Ryohei Kamura Kazuto Kinoshita Dr. Hyuma Masu Prof. Dr. Isao Azumaya Prof. Dr. Sensuke Ogoshi Prof. Dr. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3415-3425
A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes. 相似文献
105.
Takeuchi Y Nishikawa M Hachiya H Yamamoto H 《Magnetic resonance in chemistry : MRC》2005,43(8):662-664
High-resolution solid-state magic angle spinning (73)Ge NMR spectra of some organogermanium compounds were measured. Most tetrasubstituted germanes with identical substituents exhibited signals except for one case. Tetrasubstituted germanes with two kinds of different but somewhat similar substituents exhibited broad peaks. Trisubstituted germanes failed to show signals, indicating the importance of symmetry around germanium. 相似文献
106.
Hiroyuki Muramatsu Kazunori Fujisawa Yong-Il Ko Kap-Seung Yang Takuya Hayashi Morinobu Endo Cheol-Min Yang Yong Chae Jung Yoong Ahm Kim 《催化学报》2014,35(6):864-868
Nanoscale defects in the outer tube to preserve the electrical and optical features of the inner tube can be engineered to exploit the intrinsic properties of double walled carbon nanotubes (DWCNTs) for various promising applications. We demonstrated a selective way to make defects in the outer tube by the fluorination of DWCNTs followed by the thermal detachment of the F atoms at 1000 °C in argon. Fluorinated DWCNTs with different amounts of F atoms were prepared by reacting with fluorine gas at 25, 200, and 400 °C that gave the stoichiometry of CF0.20, CF0.30, and CF0.43, respectively. At the three different temperatures used, we observed preservation of the coaxial morphology in the fluorinated DWCNTs. For the DWCNTs fluorinated at 25 and 200 °C, the strong radial breathing modes (RBMs) of the inner tube and weakened RBMs of the outer tube indicated selective fluorine attachment onto the outer tube. However, the disappearance of the RBMs in the Raman spectrum of the DWCNTs fluorinated at 400 °C showed the introduction of F atoms onto both inner and outer tubes. There was no significant change in the morphology and optical properties when the DWCNTs fluorinated at 25 and 200 °C were thermally treated at 1000 °C in argon. However, in the case of the DWCNTs fluorinated at 400 °C, the recovery of strong RBMs from the inner tube and weakened RBMs from the outer tube indicated the selective introduction of substantial defects on the outer tube while preserving the original tubular shape. The thermal detachment of F atoms from fluorinated DWCNTs is an efficient way to make highly defective outer tubes for preserving the electrical conduction and optical activity of the inner tubes. 相似文献
107.
Ryo Kimura Hikaru Kuramochi Pengpeng Liu Takuya Yamakado Atsuhiro Osuka Tahei Tahara Shohei Saito 《Angewandte Chemie (International ed. in English)》2020,59(38):16430-16435
Flapping fluorophores (FLAP) with a flexible 8π ring are rapidly gaining attention as a versatile photofunctional system. Here we report a highly photostable “flapping peryleneimide” with an unprecedented fluorogenic mechanism based on a bent‐to‐planar conformational change in the S1 excited state. The S1 planarization induces an electronic configurational switch, almost quenching the inherent fluorescence (FL) of the peryleneimide moieties. However, the FL quantum yield is remarkably improved with a prolonged lifetime upon a slight environmental change. This fluorogenic function is realized by sensitive π‐conjugation design, as a more π‐expanded analogue does not show the planarization dynamics. With strong visible‐light absorption, the FL lifetime response synchronized with the flexible flapping motion is useful for the latest optical techniques such as FL lifetime imaging microscopy (FLIM). 相似文献
108.
Total Synthesis of 11‐Saxitoxinethanoic Acid and Evaluation of its Inhibitory Activity on Voltage‐Gated Sodium Channels 下载免费PDF全文
Chao Wang Mana Oki Toru Nishikawa Daisuke Harada Prof. Dr. Mari Yotsu‐Yamashita Prof. Dr. Kazuo Nagasawa 《Angewandte Chemie (International ed. in English)》2016,55(38):11600-11603
11‐Saxitoxinethanoic acid (SEA) is a member of the saxitoxin (STX) family of paralytic shellfish poisons, and contains an unusual C?C bond at the C11 position. Reported herein is a total synthesis of SEA. The key to our synthesis lies in a Mukaiyama aldol condensation reaction of silyl enol ether with glyoxylate in the presence of an anhydrous fluoride reagent, [Bu4N][Ph3SnF2], which directly constructs the crucial C?C bond at the C11 position in SEA. The NaVCh‐inhibitory activities of SEA and its derivatives were evaluated by means of cell‐based assay. SEA showed an IC50 value of (47±12) nm , which is approximately twice as potent as decarbamoyl‐STX (dcSTX). 相似文献
109.
Photoinduced disruption of a sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelle is triggered by a Malachite Green leuconitrile derivative (MGL). UV irradiation of MGL solubilized in an AOT-water-chloroform mixture creates a cationic surfactant that interacts electrostatically with the anionic AOT. We investigated the disruption of the reverse micelle by using proton nuclear magnetic resonance spectroscopy and found that UV irradiation of MGL decreases the number of water molecules solubilized in the interior of the AOT reverse micelles. Furthermore, the photoinduced disruption of the reverse micelle is shown to release ribonuclease A, which is trapped in the water in the interior of the AOT reverse micelle. This photoinduced release may offer a desirable transport system of biopolymers. 相似文献
110.
Ehsan Jazaeri Liyuan Zhang Xungai Wang Takuya Tsuzuki 《Cellulose (London, England)》2011,18(6):1481-1485
The possibility of fabricating carbon nanofibers from cellulose nanofibers was investigated. Cellulose nanofiber of ~50 nm
in diameter was produced using ball milling in an eco-friendly manner. The effect of the drying techniques of cellulose nanofibers
on the morphology of carbon residue was studied. After pyrolysis of freeze-dried cellulose nanofibers below 600 °C, amorphous
carbon fibers of ~20 nm in diameter were obtained. The pyrolysis of oven-dried precursors resulted in the loss of original
fibrous structures. The different results arising from the two drying techniques are attributed to the difference in the spatial
distance between cellulose nanofiber precursors. 相似文献