全文获取类型
收费全文 | 3007篇 |
免费 | 88篇 |
国内免费 | 10篇 |
专业分类
化学 | 2253篇 |
晶体学 | 33篇 |
力学 | 36篇 |
数学 | 142篇 |
物理学 | 641篇 |
出版年
2023年 | 13篇 |
2021年 | 20篇 |
2020年 | 46篇 |
2019年 | 51篇 |
2018年 | 39篇 |
2017年 | 21篇 |
2016年 | 60篇 |
2015年 | 53篇 |
2014年 | 73篇 |
2013年 | 151篇 |
2012年 | 155篇 |
2011年 | 182篇 |
2010年 | 106篇 |
2009年 | 87篇 |
2008年 | 158篇 |
2007年 | 149篇 |
2006年 | 146篇 |
2005年 | 145篇 |
2004年 | 123篇 |
2003年 | 131篇 |
2002年 | 98篇 |
2001年 | 70篇 |
2000年 | 70篇 |
1999年 | 38篇 |
1998年 | 23篇 |
1997年 | 30篇 |
1996年 | 29篇 |
1995年 | 24篇 |
1994年 | 31篇 |
1993年 | 40篇 |
1992年 | 37篇 |
1991年 | 46篇 |
1990年 | 46篇 |
1989年 | 31篇 |
1988年 | 42篇 |
1987年 | 43篇 |
1986年 | 35篇 |
1985年 | 59篇 |
1984年 | 43篇 |
1983年 | 21篇 |
1982年 | 32篇 |
1981年 | 35篇 |
1980年 | 22篇 |
1979年 | 35篇 |
1978年 | 33篇 |
1977年 | 41篇 |
1976年 | 31篇 |
1975年 | 22篇 |
1974年 | 17篇 |
1973年 | 21篇 |
排序方式: 共有3105条查询结果,搜索用时 125 毫秒
1.
Shotaro Yoshida Kensuke Sumomozawa Kuniaki Nagamine Matsuhiko Nishizawa 《Macromolecular bioscience》2019,19(6)
A hydrogel‐based microchamber with organic electrodes for efficient electrical stimulations of human induced pluripotent stem cell‐derived cardiomyocytes (hiPSC‐CMs) is described. The microchamber is made from molecularly permeable, optically transparent, and electrically conductive polyvinyl alcohol (PVA) hydrogel and highly capacitive carbon electrode modified with poly(3,4‐ethylenedioxythiophene) (PEDOT). Spheroids of hiPSC‐CMs are cultured in microchambers, and electrically stimulated by the electrode for maturation. The large interfacial capacitance of the electrodes enables several days of electrical stimulation without generation of cytotoxic bubbles even when the electrodes are placed near the spheroids. The spheroids can be cultivated in the closed microchambers because of the permeated nutrients through the hydrogel, thus the spheroids are stably addressable and the culture medium around the sealed microchambers can be simply exchanged. Synchronized beating of the spheroids can be optically analyzed in situ, which makes it possible to selectively collect electrically responsive cells for further use. As the hydrogel is electrically conductive, the amount of electrical charge needed for maturing the spheroids can be reduced by configuring electrodes on the top and the bottom of the microchamber. The bioreactor will be useful for efficient production of matured hiPSC‐CMs for regenerative medicine and drug screening. 相似文献
2.
3.
Total Synthesis and Structure Elucidation of JBIR‐39: A Linear Hexapeptide Possessing Piperazic Acid and γ‐Hydroxypiperazic Acid Residues 下载免费PDF全文
Dr. Masahito Yoshida Naoki Sekioka Dr. Miho Izumikawa Dr. Ikuko Kozone Dr. Motoki Takagi Dr. Kazuo Shin‐ya Prof. Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):3031-3041
The total synthesis and stereochemical structural elucidation of JBIR‐39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)3‐catalyzed acylation of a Piz(γ‐OTBS) derivative with piperazic acid chloride, providing the desired Piz‐Piz(γ‐OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)‐isoleucic acid at the N‐terminus, amidation with the (R)‐α‐methylserine ester at the C‐terminus, and deprotection afforded the desired (2R,8S)‐hexapeptide, which is the assumed structure of JBIR‐39. Although the spectral data of the (2R,8S)‐hexapeptide was not identical to JBIR‐39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR‐39 to be (2S,6S,8S,11R,16S,21R,26S,27S). 相似文献
4.
Reassessment of the NH4NO3 thermal decomposition technique for calibration of the N2O isotopic composition 下载免费PDF全文
5.
Daisuke Saito Dr. Tomasz Galica Prof. Dr. Eiji Nishibori Dr. Masaki Yoshida Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200703
The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N-heterocyclic carbene [Pt(CN)2(tBu-impy)] (tBu-impyH+=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor. 相似文献
6.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
7.
Lars J. Wesenberg Erika Diehl Till J. B. Zähringer Carolin Dörr Dr. Dieter Schollmeyer Dr. Akihiro Shimizu Prof. Dr. Jun-ichi Yoshida Prof. Dr. Ute A. Hellmich Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17574-17580
The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non-protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against castrate-resistant prostate cancer. Further improvement of the structure led to significantly increased cancer cell line toxicity. Thus, exploiting environmentally benign electrooxidation, we present a new versatile and powerful method based on direct C−H activation that is applicable for example the production of medicinally relevant compounds. 相似文献
8.
Nobutaka Yoshimura Dr. Atsushi Kobayashi Dr. Masaki Yoshida Prof. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16939-16946
To investigate the effect of the surface structure of dye-sensitized photocatalyst nanoparticles, we prepared three types of RuII-photosensitizer (PS)-double-layered Pt-cocatalyst-loaded TiO2 nanoparticles with different surface structures, Zr- RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, RuCP6 -Zr- RuP6 @N wt %Pt-TiO2, and RuCP2 -Zr- RuP6 @N wt %Pt-TiO2 (N=0.2, 1, and 5), and evaluated their photocatalytic H2 evolution activity in the presence of redox-reversible iodide as the electron donor. Although the driving force of the electron injection from I− to the photo-oxidized RuIII PS is comparable, the activity increased in the following order: RuCP2 -Zr- RuP6 @1 wt %Pt-TiO2 < RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 < Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2. The apparent quantum yield of Zr- RuCP6 -Zr- RuP6 @1 wt %Pt-TiO2 in the first hour reached 1 %. Zeta-potential measurements suggest that the surface Zr4+-phosphate groups attracted I− anions to the nanoparticle–solution interface. Our results indicate that the surface modification of dye-sensitized photocatalysts is a promising approach to enhance photocatalytic activity with various redox mediators. 相似文献
9.
10.
Dr. Bozheng Sun Dr. Meagan S. Oakley Dr. Kota Yoshida Yanwen Yang Prof. Matteo Tommasini Dr. Chiara Zanchi Dr. Andrea Lucotti Dr. Michael J. Ferguson Dr. Frank Hampel Prof. Mariusz Klobukowski Prof. Rik R. Tykwinski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(38):e202200616
Cyclic tetraaryl[5]cumulenes ( 1 a–f ) have been synthesized and studied as a function of increasing ring strain. The magnitude of ring strain is approximated by the extent of bending of the cumulenic core as assessed by a combination of X-ray crystallographic analysis and DFT calculations. Trends are observed in 13C NMR, UV-vis, and Raman spectra associated with ring strain, but the effects are small. In particular, the experimental HOMO-LUMO gap is not appreciably affected by bending of the [5]cumulene framework from ca. 174° (λmax=504 nm) in 1 a to ca. 178° (λmax=494 nm) in 1 f . 相似文献