全文获取类型
收费全文 | 471篇 |
免费 | 37篇 |
专业分类
化学 | 370篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 38篇 |
物理学 | 91篇 |
出版年
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 13篇 |
2020年 | 14篇 |
2019年 | 14篇 |
2018年 | 15篇 |
2017年 | 10篇 |
2016年 | 18篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 30篇 |
2012年 | 38篇 |
2011年 | 43篇 |
2010年 | 32篇 |
2009年 | 36篇 |
2008年 | 33篇 |
2007年 | 33篇 |
2006年 | 31篇 |
2005年 | 20篇 |
2004年 | 20篇 |
2003年 | 8篇 |
2002年 | 11篇 |
2001年 | 5篇 |
2000年 | 8篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有508条查询结果,搜索用时 312 毫秒
91.
Kobayashi K Kitagawa R Yamada Y Yamanaka M Suematsu T Sei Y Yamaguchi K 《The Journal of organic chemistry》2007,72(9):3242-3246
Tetrakis(4-hydroxyphenyl)-cavitand 1 and tetra(4-pyridyl)-cavitand 2 self-assemble into a heterodimeric capsule 1.2 via four ArOH...pyridyl hydrogen bonds in CDCl3. The 1.2 expresses the orientational isomerism of an encapsulated unsymmetrical guest with high orientational selectivity because the electronic environment of the 1 unit is different from that of the 2 unit. For p-ethoxyiodobenzene and 2-iodo-6-methoxynaphthalene encapsulated in 1.2, the iodo group is specifically oriented to the cavity of the 2 unit. The orientational isomeric selectivity for methyl p-acetoxybenzoate and methyl p-ethoxybenzoate within 1.2 is 1:0.11 and 1:<0.05, respectively, wherein the methyl ester group is preferentially oriented to the cavity of the 2 unit. The delicate balance among electrostatic potential repulsion, CH-pi interaction, or CH-halogen (halogen-pi) interaction, in 1.2-guest assembly influences the orientational isomeric selectivity of unsymmetrical guests within 1.2. 相似文献
92.
Nakayama Y Okahashi R Iwai R Uchida K 《Langmuir : the ACS journal of surfaces and colloids》2007,23(15):8206-8211
With a view to reducing the thrombogenic potential of artificial blood-contact devices and natural tissues, we developed a novel aqueous antithrombogenic coating material, comprising a heparin bioconjugate that incorporated a thermoresponsive cationic polymer as a surfactant. The polymer was prepared by the sequential steps of initiator-transfer agent-terminator (iniferter)-based living radical photopolymerization of N-[3-(dimethylamino)propyl]acrylamide, followed by the polymerization of N-isopropylacrylamide from tetra(N,N-diethyldithiocarbamylmethyl)benzene as a multifunctional iniferter. The polymer obtained possessed four branched chains, each consisting of a cationic PDMAPAAm block (Mn: ca. 3000 g.mol(-1)) forming an inner domain for heparin binding and a thermoresponsive PNIPAM block (Mn: ca. 6000 g.mol(-1)) forming an outer domain for surface fixation; bioconjugation of the polymer with heparin occurred immediately upon simple mixing in an aqueous medium. Because the lower critical solution temperature of the heparin bioconjugate was approximately 35 degrees C, it could be coated from an aqueous solution at room temperature. The excellent adsorptivity and high durability of the coating below 37 degrees C was demonstrated on several generally used polymers by wettability measurement and surface chemical compositional analysis, and on collagen sheets and rat skin tissue by heparin staining. Blood coagulation was significantly prevented on the heparin bioconjugate-coated surfaces. The thermoresponsive bioconjugate developed therefore appeared to satisfy the initial requirements for a biocompatible aqueous coating material. 相似文献
93.
Ryosuke Nakahara Satomi Kashitani Kumi Hayakawa Yuuki Kitani Takako Yamaguchi Yoshikazu Fujita 《Journal of fluorescence》2009,19(5):769-775
A fluorophotometric method for the determination of hydrogen peroxide (H2O2) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent
lactoid fluorescein, by H2O2 to give highly fluorescein fluorescence emission. In the determination of H2O2, the calibration curve exhibited linearity over the H2O2 concentration range of 1.5–310 ng mL−1 at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL−1, 30.8 ng mL−1, and for 308 ng mL−1 of H2O2, respectively. The detection limit for H2O2 was 1.9 ng mL−1 six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such
as singlet oxygen (1O2), hydroxyl radical (•OH), peroxynitrite (ONOO−) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery
tests of H2O2 in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory. 相似文献
94.
Hitomi Kitagawa Ryosuke Kitagawa Masamichi Yamanaka Kenji Kobayashi 《Tetrahedron》2009,65(35):7234-914
Tetra(4-pyridyl)-cavitand 1 and tetrakis(4-hydroxyphenyl)-cavitand 2 self-assemble into a heterodimeric capsule 1·2 via four PhOH?pyridyl hydrogen bonds in CDCl3, wherein one molecule of 1,4-disubstituted-benzene as a guest is encapsulated to form a ternary complex, guest@(1·2). The X-ray crystallographic analysis of (methyl p-ethoxybenzoate)@(1·2) confirmed that the methyl ester and ethoxy groups of the encapsulated guest are oriented to the cavity ends of the 1 and 2 units, respectively. The scope and limitation of guest encapsulation in 1·2, including guest-binding selectivity and orientational isomeric selectivity, are described from the viewpoint of size complementarity and CH-π, CH-halogen, and halogen-π interactions between guest and the cavity of 1·2. 相似文献
95.
96.
Yoshihiro Nishimoto Ryosuke Moritoh Makoto Yasuda Dr. Akio Baba Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(25):4577-4580
InBr 3 promotes the addition of ketene silyl acetals to monosubstituted alkynes to afford 2,2‐disubstituted alkenylindium compounds in high regio‐ and stereoselectivity (see scheme). In addition, the alkenylindium derivatives have been subsequently coupled with iodobenzene in the presence of a palladium catalyst.
97.
Shunsuke Murai Ryosuke Hattori Tomohiko Matoba Koji Fujita Katsuhisa Tanaka 《Journal of Non》2011,357(11-13):2259-2263
Wavelength-selective enhancement of optical birefringence has been observed in a tellurite glass containing silver nanoparticles (Ag NPs) induced via thermal poling. The birefringence appears as an optical rotation of linearly polarized light; a large optical rotation is observed at around the wavelength of localized surface plasmon resonance (LSPR) of Ag NPs. The optic axis is oriented along the electric field applied during the thermal poling, suggesting that birefringence induced in the glass matrix through the thermal poling is drastically enhanced by the NPs at around the LSPR. Because of the birefringence of the matrix, the wavelength of LSPR shifts depending on the polarization state of the incident light, which in turn induces the polarization dependence of the real part of the refractive index via the Kramers–Kronig relation. 相似文献
98.
In this paper, we are concerned with the effect of the domain topology on the multiplicity of solutions for some semilinear
elliptic systems involving critical Sobolev exponent. We show that if the interaction term is sufficiently small, then the
number of solutions of the system is estimated from below by 2 catΩ. The proof of this fact requires analysis of the structure
of the Nehari manifold associated with the system.
This research was partially supported by the Grant-in-Aid for Young Scientists (B), The Ministry of Education, Culture, Sports,
Science and Technology, Japan. 相似文献
99.
Yoshiaki Muroya Emiko Ishiwata Nicola Guglielmi 《Frontiers of Mathematics in China》2009,4(1):131-154
In this paper we consider some classes of difference equations, including the well-known Clark model, and study the stability
of their solutions. In order to do that we introduce a property, namely semicontractivity, and study relations between ‘semi-contractive’
functions and sufficient conditions for the solution of the difference equation to be globally asymptotically stable. Moreover,
we establish new sufficient conditions for the solution to be globally asymptotically stable, and we improve the ‘3/2 criteria’
type stability conditions.
相似文献
100.
Jiang C Lesbani A Kawamoto R Uchida S Mizuno N 《Journal of the American Chemical Society》2006,128(44):14240-14241
An ionic crystal of Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40].4H2O 1a with hydrophilic and hydrophobic channels has been designed and successfully synthesized. The guest-free phase 1b sorbs dichloromethane and water in the hydrophobic and hydrophilic channels, respectively. The rate and equilibrium amount of the dichloromethane sorption into the hydrophobic channel and those of water into the hydrophilic channel were independent of each other. The sorption properties can be applied to the channel-selective sorption and collection of hydrophobic (dichloromethane) and hydrophilic (water) molecules from the mixture. 相似文献