全文获取类型
收费全文 | 1373篇 |
免费 | 87篇 |
国内免费 | 7篇 |
专业分类
化学 | 1165篇 |
晶体学 | 8篇 |
力学 | 15篇 |
数学 | 82篇 |
物理学 | 197篇 |
出版年
2024年 | 3篇 |
2023年 | 20篇 |
2022年 | 18篇 |
2021年 | 20篇 |
2020年 | 33篇 |
2019年 | 46篇 |
2018年 | 38篇 |
2017年 | 16篇 |
2016年 | 33篇 |
2015年 | 56篇 |
2014年 | 54篇 |
2013年 | 82篇 |
2012年 | 99篇 |
2011年 | 92篇 |
2010年 | 70篇 |
2009年 | 57篇 |
2008年 | 107篇 |
2007年 | 81篇 |
2006年 | 105篇 |
2005年 | 102篇 |
2004年 | 87篇 |
2003年 | 63篇 |
2002年 | 48篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 9篇 |
1998年 | 8篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1467条查询结果,搜索用时 0 毫秒
131.
Aya Yoshimura Akihiro Nomoto Mari Uchida Hiroki Kusano Tomokazu Saeki Akiya Ogawa 《Research on Chemical Intermediates》2017,43(6):3433-3443
The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RfI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI2) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and RfI (about 1.0 mM CHCl3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate. 相似文献
132.
Kenji ArimitsuSayo Nomura Hiroki IwasakiMinoru Ozeki Masayuki Yamashita 《Tetrahedron letters》2011,52(52):7046-7048
The first total synthesis of (±)-adunctin B (1), a natural product isolated from Piper aduncum (Piperaceae) and having antibacterial activity, was achieved in 1.26% overall yield in 15 steps from 5,7-dimethoxycoumarin-3-carboxylate (8). 相似文献
133.
Matsukuma D Watanabe H Yamaguchi H Takahara A 《Langmuir : the ACS journal of surfaces and colloids》2011,27(4):1269-1274
We demonstrate the successful preparation of stable liquid marbles from various liquids. This is accomplished by using low-surface-energy poly[2-(perfluorooctyl)ethyl acrylate] (PFA-C(8)) as microparticles. The PFA-C(8) microparticles were prepared by the spontaneous self-organized microparticulation of PFA-C(8). The physical properties remained intact in the polymer morphology as confirmed by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) measurements. The extremely low surface energy of PFA-C(8) provides a high solid-liquid spreading coefficient (S(S/L)) value for various combinations of liquids. As a result, liquid marbles were obtained from various liquids, unlike the case with other fluorine polymer particles such as poly(tetrafluoroethylene) (PTFE) and poly(vinilydene fluoride) (PVDF). These results suggest that the technique is widely applicable for preparing novel functional materials. 相似文献
134.
Determination methods of halide ions (X(-) = F(-), Cl(-), Br(-) and I(-)) by electrospray ionization mass spectrometry (ESIMS) were developed, where negative ions of the ternary complexes of group-13 elements, nitrilotriacetic acid (NTA), and halides were measured. In particular, these halides were simultaneously determined by measuring [InX(nta)](-), and the limits of detection (LODs) were 1.1 μmol dm(-3) for F(-), 0.32 μmol dm(-3) for Cl(-), 3.8 nmol dm(-3) for Br(-), and 1.6 nmol dm(-3) for I(-), respectively. This approach was extended to the determination of CN(-), where the ternary complex of Cu(II), CN(-) and 4-(2-pyridylazo)resorcinol (PAR), i.e., [(63)Cu(II)(CN)(par)](-) (m/z 302) was measured. The LOD for CN(-) was 20 nmol dm(-3). 相似文献
135.
New structurally constrained BODIPY dyes having electron-donating substituents were synthesized. As the key compounds for the construction of the BODIPY dyes, 1′H-spiro-[fluorene-9,4′-indeno[1,2-b]pyrrole] (sp-FIP) derivatives with electron-donating groups, such as OMe and NMe2 at its 6′-position, were prepared using palladium-catalyzed intramolecular direct C-H arylation of a pyrrole moiety. The resulting BODIPY dyes showed bathochromic shift in absorption and fluorescence spectra in comparison to the unsubstituted analogs. Furthermore, pH-dependent reversible spectrum changes of the BODIPY dye were observed with the addition of trifluoroacetic acid (TFA) and subsequent addition of i-Pr2NEt. 相似文献
136.
Mitsumoto K Oshiro E Nishikawa H Shiga T Yamamura Y Saito K Oshio H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9612-9618
Cyanide‐bridged metal complexes of [Fe8M6(μ‐CN)14(CN)10 (tp)8(HL)10(CH3CN)2][PF6]4?n CH3CN?m H2O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P21/n. They have tetradecanuclear cores composed of eight low‐spin (LS) FeIII and six high‐spin (HS) MII ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐FeII)3(LS‐FeIII)5(HS‐CoII)3(LS‐CoIII)3] and the [(LS‐FeIII)8(HS‐CoII)6] states. 相似文献
137.
138.
Imada Y Iida H Kitagawa T Naota T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(21):5908-5920
A versatile reducing agent, diimide, can be generated efficiently by the aerobic oxidation of hydrazine with neutral and cationic synthetic flavin catalysts 1 and 2. This technique provides a convenient and safe method for the aerobic reduction of olefins, which proceeds with 1 equiv of hydrazine under an atmosphere of O(2) or air. The synthetic advantage over the conventional gas-based method has been illustrated through high hydrazine efficiency, easy and safe handling, and characteristic chemoselectivity. Vitamin B(2) derivative 6 acts as a highly practical, robust catalyst for this purpose because of its high availability and recyclability. Association complexes of 1b with dendritic 2,5-bis(acylamino)pyridine 15 exhibit unprecedented catalytic activities, with the reduction of aromatic and hydroxy olefins proceeding significantly faster when a higher-generation dendrimer is used as a host pair for the association catalysts. Contrasting retardation is observed upon similar treatment of non-aromatic or non-hydroxy olefins with the dendrimer catalysts. Control experiments and kinetic studies revealed that these catalytic reactions include two independent, anaerobic and aerobic, processes for the generation of diimide from hydrazine. Positive and negative dendrimer effects on the catalytic reactions have been ascribed to the specific inclusion of hydrazine and olefinic substrates into the enzyme-like reaction cavities of the association complex catalysts. 相似文献
139.
140.
Anomalous dielectric behavior and thermal motion of water molecules confined in channels of porous coordination polymer crystals 总被引:1,自引:0,他引:1
Zhou B Kobayashi A Cui HB Long LS Fujimori H Kobayashi H 《Journal of the American Chemical Society》2011,133(15):5736-5739
Guest water molecules confined in channels of porous coordination polymer crystals [Ln(2)Cu(3)(IDA)(6)]·nH(2)O (Ln = La, Nd, Sm, Gd, Ho, Er; IDA = [NH(CH(2)COO)(2)](2-); n ≈ 9) exhibited large dielectric constants (ε) and antiferroelectric behaviors at high temperatures (e.g., ε(Sm) ≈ 1300 at 400 K). In addition, plots of the temperature dependence of ε showed broad peaks at ~170 K, below which ε became very small. These puzzling temperature dependences of ε are consistent with the results of molecular dynamics simulations, suggesting the "freezing of thermal motion" of water molecules at ~170 K. 相似文献