全文获取类型
收费全文 | 3334篇 |
免费 | 811篇 |
国内免费 | 417篇 |
专业分类
化学 | 3024篇 |
晶体学 | 99篇 |
力学 | 1篇 |
综合类 | 7篇 |
物理学 | 1431篇 |
出版年
2024年 | 6篇 |
2023年 | 30篇 |
2022年 | 119篇 |
2021年 | 134篇 |
2020年 | 213篇 |
2019年 | 154篇 |
2018年 | 105篇 |
2017年 | 105篇 |
2016年 | 267篇 |
2015年 | 199篇 |
2014年 | 259篇 |
2013年 | 345篇 |
2012年 | 250篇 |
2011年 | 240篇 |
2010年 | 208篇 |
2009年 | 221篇 |
2008年 | 229篇 |
2007年 | 201篇 |
2006年 | 187篇 |
2005年 | 169篇 |
2004年 | 173篇 |
2003年 | 134篇 |
2002年 | 148篇 |
2001年 | 76篇 |
2000年 | 54篇 |
1999年 | 45篇 |
1998年 | 52篇 |
1997年 | 47篇 |
1996年 | 36篇 |
1995年 | 39篇 |
1994年 | 48篇 |
1993年 | 20篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 9篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有4562条查询结果,搜索用时 15 毫秒
101.
Photochromism of 1′,3′,3′-trimethyl-6-piperidinospiro [indoline-2′,3-3H-naphth [2,1-b][1,4]-oxazine]
The effect of the piperidine substituent on the spectral and photochromic properties of spiro(indoline-naphthoxazines) (SINO) in different solvents is studied. The introduction of this substituent into the naphthoxazine fragment of SINO results in the appearance of fluorescence of the initial formA of SINO at low temperatures. This fluorescence gradually disappears as the temperature increases. The temperature and concentration dependences of the spectral parameters of photoinduced formB of SINO make it possible to assume thatB molecules aggregate in non-polar solvents. In all solvents studied, form B, unlike the photoinduced form of the non-substituted spiro naphthoxazine, is stabilized as a bipolar ion with a positive charge on the nitrogen atom of the piperidine substituent. The increase in the rate of thermal decolorization as the medium polarity increases is explained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 684–688, April, 1995.The authors are grateful to the Belarus' Foundation for Basic Research for financial support of this work. 相似文献
102.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):149-158
Two Dy–Mn polymers, {[Dy(L1)3Mn1.5(H2O)3]?3.125 H2O}n ( 1 , L1=pyridine‐2,6‐dicarboxylic acid) and {[Dy(L2)3Mn1.5(H2O)6]?8.25 H2O}n ( 2 , L2 = 4‐hydroxylpyridine‐2,6‐dicarboxylic acid), with high symmetry (S6) have been prepared. Polymer 1 has a nanoporous 3D framework with channel of about 17.6 Å diameter, while 2 has a honeycomb‐type 2D structure with the cavity of approximately 14.4 Å diameter. In the construction of multidimensional porous polymers with 3d–4f mixed metals, it is the first observation that a ligand substituent effect leads to dramatic differences in the structures formed. Luminescent studies reveal that the emission intensities of 1 and 2 increase significantly upon the addition of Mg2+, whereas the introduction of other metal ions leaves the intensity unchanged or even weakens it; hence, both of them may serve as good candidates of Mg2+ luminescent probes. To our knowledge, complex 1 is also the first example of a 3d–4f metal‐based nanoporous polymer to exhibit luminescent selectivity for Mg2+. Magnetic susceptibility measurements reveal a rather rare ferromagnetic interaction in 2 . Thermal gravimetric analyses and powder X‐ray diffraction investigations have also been performed, suggestive of high thermal stability of 1 . 相似文献
103.
The interactions of [Pt(CNN)(4-dpt)]PF(6), (1; 4-dpt=2,4-diamino-6-(4-pyridyl)-1,3,5-triazine, HCNN=6-phenyl-2,2'-bipyridine) with double-stranded DNA, poly(dA-dT)(2), and poly(dG-dC)(2) were examined by spectroscopic, electrophoretic, and hydrodynamic methods. The spectroscopic data were analyzed with McGhee, van't Hoff, and Gibbs-Helmholtz equations. In a comparative study, [Pt(CNN)(py)]PF(6) (2; py=pyridine) was prepared and the nature of its binding towards DNA was investigated [preliminary results: ChemBioChem 2003, 4, 62-68]. For reactions with calf thymus DNA at 20 degrees C, the intrinsic binding constants for 1 and 2 are (4.6+/-0.2)x10(5) and (2.3+/-0.3)x10(4) mol(-1) dm(3), respectively. Results of DNA-binding reactions revealed that 1 and 2 preferentially bind to the AT sequence of duplex DNA. Intercalation is the preferred binding mode for 2, whereas both intercalation and minor-groove binding are observed for 1. Complex 1 is cytotoxic against a number of carcinoma cell lines, including KB-3-1, CNE-3, and HepG2, and remains potent against multidrug- or cisplatin-resistant KB-V-1 and CNE1 cell lines, for which the resistance ratios are 1.6 and 1.5, respectively. Importantly, 1 is almost an order of magnitude less toxic to the normal cell line CCD-19Lu (IC(50)=176+/-1.7 microM) and it selectively induced apoptosis leading to cancer cell death with less than 5 % detectable necrosis. 相似文献
104.
Stefan Lis Sławomir But 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(1-2):225-231
The heteropolytungstates [(Na)P5W30O110]4– (I), [(Na)Sb9W21O86]18– (II) and [(Na)As4W40O140]27– (III) and the monovacant Keggin structure of the general formula [XW11–xMoxO39]n– (X-Si, P; n = 7 for P and 8 for Si) (IV) as well as their europium(III) complexes were studied. The structures of I–IV as well as the europium(III) encrypted [(Eu)P5W30O110]12– (VI), [(Eu)Sb9W21O86]16– (VII), [(Eu)As4W40O140]25– (VIII) and sandwiched [Eu(XW11–xMoxO39)2]n– (n =11 for P and n = 13 for Si) (V) complexes were synthesized and spectroscopically characterized. The complexes were studied using UV-Vis absorption and luminescence, as well as the laser-induced europium ion luminescence spectroscopy. Absorption spectra of Nd(III) were used to characterize the complexes formed. Excitation and emission spectra of Eu(III) were obtained for solid complexes and their solutions. The relative luminescence intensities of the Eu(III) ion, expressed as the ratio of the two strongest lines at 594 nm and 615 nm, = I615/I594, which is sensitive to the environment of the primary coordination sphere about the Eu(III) ion, was calculated. In the case of the sandwiched [Eu(XW11–xMoxO39)2]n– complexes a linear dependence of the luminescence quantum yield of Eu(III) ion, , (calculated using [Ru(bpy)3]Cl2 as a standard) on the content of Mo (number of atoms, x) in the [Eu(XW11–xMoxO39)2]n– structure was observed. 相似文献
105.
Yoshikuni Uchida Masao Yoshida Osamu Nishiara Kazunori Matsui 《Journal of Sol-Gel Science and Technology》2003,26(1-3):177-180
Silica gels doped with Cu2+ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu2+. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu+ monomer and dimer emissions, respectively. These results indicate that Cu2+ ions are reduced to Cu+. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu2+ ions. 相似文献
106.
107.
Kyoichi Hanada Juntaro Nogami Prof. Dr. Kazunori Miyamoto Norihiko Hayase Dr. Yuki Nagashima Yusuke Tanaka Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9313-9319
The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions. 相似文献
108.
Two supramolecular complexes, [Cd(bimb)2Cl2] (1) and [Cd(bimb)(DMF)Cl2]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl2·2.5H2O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks. 相似文献
109.
110.
Host–Guest Chemistry between Perylene Diimide (PDI) Derivatives and 18‐Crown‐6: Enhancement in Luminescence Quantum Yield and Electrical Conductivity
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)
P. Lasitha Prof. Dr. Edamana Prasad 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10558-10564
Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation‐induced quenching of emission from the system. Host–guest chemistry is one of the best‐known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18‐crown‐6 (18‐C‐6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18‐C‐6 formed complexes with amino‐substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI ? 18‐C‐6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60–70 %) from the PDI derivatives. More importantly, the host–guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self‐assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10?5 S cm?1. 相似文献