全文获取类型
收费全文 | 1333篇 |
免费 | 17篇 |
国内免费 | 7篇 |
专业分类
化学 | 1120篇 |
晶体学 | 12篇 |
力学 | 6篇 |
综合类 | 1篇 |
数学 | 37篇 |
物理学 | 181篇 |
出版年
2021年 | 8篇 |
2019年 | 13篇 |
2018年 | 11篇 |
2017年 | 7篇 |
2016年 | 12篇 |
2015年 | 10篇 |
2014年 | 19篇 |
2013年 | 56篇 |
2012年 | 49篇 |
2011年 | 44篇 |
2010年 | 35篇 |
2009年 | 37篇 |
2008年 | 53篇 |
2007年 | 73篇 |
2006年 | 66篇 |
2005年 | 68篇 |
2004年 | 61篇 |
2003年 | 68篇 |
2002年 | 74篇 |
2001年 | 20篇 |
2000年 | 17篇 |
1999年 | 27篇 |
1998年 | 12篇 |
1997年 | 20篇 |
1996年 | 13篇 |
1995年 | 16篇 |
1994年 | 12篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 15篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 10篇 |
1985年 | 35篇 |
1984年 | 39篇 |
1983年 | 23篇 |
1982年 | 26篇 |
1981年 | 24篇 |
1980年 | 27篇 |
1979年 | 26篇 |
1978年 | 21篇 |
1977年 | 25篇 |
1976年 | 25篇 |
1975年 | 16篇 |
1974年 | 20篇 |
1973年 | 12篇 |
1972年 | 13篇 |
1967年 | 5篇 |
排序方式: 共有1357条查询结果,搜索用时 12 毫秒
71.
The influence of the species of counterion on the polyelectrolyte behavior and the conformation of poly-L -methionine S-methylsulfonium salts in aqueous solution was studied by viscometric, electrochemical, and optical measurements. The degree of binding of small counterions to charged polyions increases in the sequence: chloride ? bromide < iodide < thiocyanate. The conformations of chloride and bromide salts are independent of polymer concentration. On the contrary, iodide and thiocyanate salts indicate a conformational transition, probably from a random-coil conformation to an intermolecularly stabilized β-form, with the increase of polymer concentration. The results suggest the existence of a strong specific interaction between counterion and macroion in iodide and thiocyanate salt solutions at high polymer concentration. 相似文献
72.
Nakatani K Hagihara S Sando S Sakamoto S Yamaguchi K Maesawa C Saito I 《Journal of the American Chemical Society》2003,125(3):662-666
The binding of a dimeric form of the 2-amino-1,8-naphthyridine derivative (naphthyridine dimer) to a human telomeric sequence, TTAGGG, was investigated by UV melting, CD spectra, and CSI-MS measurements. Both the 9-mer d(TTAGGGTTA) and the 15-mer d(TTAGGGTTAGGGTTA) showed apparent melting temperatures (T(m)) of 45.6 and 63.6 degrees C, respectively, in the presence of naphthyridine dimer (30 microM) in sodium cacodylate buffer (50 mM, pH 7.0) containing 100 mM NaCl. The CD spectra at 235 and 255 nm of the 9-mer increased in intensity accompanied with strong induced CDs at 285 and 340 nm upon complex formation with naphthyridine dimer. UV titration of the binding of naphthyridine dimer to the 9-mer at 320 nm showed a hypochromism of the spectra. A Scatchard plot of the data showed the presence of multiple binding sites with different association constants. Cold spray ionization mass spectrometry of the complex between naphthyridine dimer and the 9-mer clearly showed that one to three molecules of the ligand bound to the dimer duplex of the 9-mer. Telomeric repeat elongation assay showed that the binding of naphthyridine dimer to the telomeric sequence inhibits the elongation of the sequence by telomerase. 相似文献
73.
Two-dimensional infrared (2D IR) spectroscopy is used to study atactic polystyrene. 2D IR is a technique based on time-resolved detection of IR signals in response to an external perturbation, such as mechanical strain. Since different chemical functional groups respond to the applied perturbation at unique and often different rates, characteristic time-dependent variations of the IR-band intensities are observed. Correlation analysis of the dynamic variation of the IR signals yields a new spectrum defined by two independent wave numbers. Peaks located on a 2D IR spectral plane imply interactions and connectivities among chemical functional groups. By spreading convoluted IR bands over two dimensions, the spectral resolution is also greatly enhanced. 相似文献
74.
Isao Takahashi Fumika Morita Shunsuke Kusagaya Haruhiko Fukaya Osamu Kitagawa 《Tetrahedron: Asymmetry》2012,23(24):1657-1662
In the presence of an (R)-MOP-Pd2(dba)3 catalyst, the reaction of ortho-tert-butylaniline with 2-bromophenyl arylethynyl ketone proceeded via a tandem amination (1,4-addition of aniline to an ynone and subsequent intramolecular Buchwald–Hartwig amination) to afford axially chiral N-(2-tert-butylphenyl)-2-aryl-4-quinolinone derivatives with moderate enantioselectivity (up to 72% ee). 相似文献
75.
Xiongchao Lin Keiko Ideta Jin Miyawaki Yusuke Nishiyama Isao Mochida Seong‐Ho Yoon 《Magnetic resonance in chemistry : MRC》2012,50(4):289-294
A general strategy of structural analysis of alumina silicate by combining various solid‐state NMR measurements such as single pulse, multi‐quantum magic angle spinning, double‐quantum homo‐nuclear correlation under magic angle spinning (DQ‐MAS), and cross‐polarization hetero‐nuclear correlation (CP‐HETCOR) was evaluated with the aid of high magnetic field NMR (800 MHz for 1H Larmor frequency) by using anorthite as a model material. The high magnetic field greatly enhanced resolution of 27Al in single pulse, DQ‐MAS, and even in triple‐quantum magic angle spinning NMR spectra. The spatial proximities through dipolar couplings were probed by the DQ‐MAS methods for homo‐nuclear correlations between both 27Al–27Al and 29Si–29Si and by CP‐HETCOR for hetero‐nuclear correlations between 27Al–29Si in the anorthite framework. By combining various NMR methodologies, we elucidated detailed spatial correlations among various aluminum and silicon species in anorthite that was hard to be determined using conventional analytical methods at low magnetic field. Moreover, the presented approach is applicable to analyze other alumina‐silicate minerals. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
76.
Prof. Kengo Hanaya Kaho Yamoto Prof. Kazuaki Taguchi Prof. Kazuaki Matsumoto Prof. Shuhei Higashibayashi Prof. Takeshi Sugai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201677
The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity. 相似文献
77.
Ayumi Suzuki Dr. Yuichiro Mutoh Dr. Noriko Tsuchida Chi-Wai Fung Dr. Shoko Kikkawa Prof. Isao Azumaya Prof. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3795-3802
Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H2IMes)(CNCH2Ts)][BArF4] (Cp=η5-C5H5−; H2IMes=1,3-dimesitylimidazolin-2-ylidene; ArF=3,5-(CF3)2C6H3). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability. 相似文献
78.
Md. Abdur Razzaque Sarker Satoshi WatauchiMasanori Nagao Takashi WatanabeIsamu Shindo Isao Tanaka 《Physica C: Superconductivity and its Applications》2012,472(1):87-91
Large single crystals of La2−xSrxCuO4 (LSCO) high-Tc superconductors were grown by the infrared heating floating zone (IR-FZ) method using a tilting-mirror-type image furnace. The maximum diameter of the LSCO crystals increased to 10 mm in the tilting-mirror-type image furnace from 6 mm in the conventional image furnace. CuO rich feeds were required for the crystal growth using the tilting-mirror-type image furnace to compensate for the lack of CuO caused by the significant evaporation of CuO during the growth. The evaporation of CuO was affected by the tilting angle of the mirrors of the image furnace and by feed diameter. The optimized growth conditions were as follows: mirror tilting angle, 20°; feed diameter, 10 mm∅; and feed composition 50.7 mol% CuO. 相似文献
79.
Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1984-1996
We have synthesized eight possible diastereoisomers 3 a – h of the C79–C97 fragment of symbiodinolide ( 1 ) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the 13C NMR chemical shifts of the natural product 1 and the synthetic products 3 a – h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1 ) is that represented in 3 a or f . We have stereodivergently synthesized eight possible diastereoisomers of the C94–C104 fragment 4 a – h , and we have compared their 13C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e . By combining the stereostructural outcomes of the C79–C97 and C94–C104 fragments, we have proposed four candidate compounds of the C79–C104 fragment 2 a – d . We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015 , DOI: 10.1002/chem.201503880) by a Julia–Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the 13C NMR chemical shifts of natural symbiodinolide ( 1 ) with those of the synthetic products 2 a – d , we have reassigned the stereostructure of the C79–C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b . 相似文献
80.
Sun-Chan Jeong Ichiro Katayama Hirokane Kawakami Yutaka Watanabe Hironobu Ishiyama Nobuaki Imai Yoshikazu Hirayama Hiroari Miyatake Masao Sataka Hiroyuki Sugai Satoru Okayasu Shin-Ichi Ichikawa Katsuhisa Nishio Shinichi Mitsuoka Takamitsu Nakanoya Takashi Hashimoto Takanori Hashimoto Masahito Yahagi 《Solid State Ionics》2009,180(6-8):626-630
The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of 8Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects. 相似文献