全文获取类型
收费全文 | 1420篇 |
免费 | 40篇 |
国内免费 | 3篇 |
专业分类
化学 | 1031篇 |
晶体学 | 18篇 |
力学 | 21篇 |
数学 | 64篇 |
物理学 | 329篇 |
出版年
2023年 | 4篇 |
2022年 | 18篇 |
2021年 | 17篇 |
2020年 | 19篇 |
2019年 | 21篇 |
2018年 | 11篇 |
2017年 | 13篇 |
2016年 | 23篇 |
2015年 | 17篇 |
2014年 | 42篇 |
2013年 | 64篇 |
2012年 | 83篇 |
2011年 | 81篇 |
2010年 | 40篇 |
2009年 | 51篇 |
2008年 | 101篇 |
2007年 | 83篇 |
2006年 | 97篇 |
2005年 | 90篇 |
2004年 | 81篇 |
2003年 | 61篇 |
2002年 | 77篇 |
2001年 | 24篇 |
2000年 | 20篇 |
1999年 | 15篇 |
1998年 | 17篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 19篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 11篇 |
1990年 | 17篇 |
1989年 | 13篇 |
1988年 | 16篇 |
1987年 | 13篇 |
1986年 | 18篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 12篇 |
1982年 | 5篇 |
1981年 | 14篇 |
1980年 | 14篇 |
1979年 | 19篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1973年 | 3篇 |
排序方式: 共有1463条查询结果,搜索用时 0 毫秒
1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
2.
Surface texturing has been recognized as an effective means to improve the tribological performances of sliding surfaces. Usually, generation additional hydrodynamic pressure to increase the load carrying capacity is regarded as the most significant effect of surface texture. In the case of silicon carbide sliding against identical material in water, the experimental results indicate that surface texture is also helpful to improve the running-in progress to smooth the contact surfaces, showing another reason to result in low friction. Based on the consideration of enhancing the generation of hydrodynamic pressure and improving running-in progress, a surface texture pattern, which was combined with large (circle, 350 μm in diameter) and small (rectangular, 40 μm in length) dimples, was designed to maximize the texture effect on the load carrying capacity of SiC surfaces sliding in water. The friction coefficient of such textured surface was evaluated and compared with that of untextured and those only with large or small dimples only. The friction reduction mechanisms of the patterns with different dimples in size are discussed. 相似文献
3.
Shigeyuki Toki Igors Sics Benjamin S. Hsiao Syozo Murakami Masatoshi Tosaka Sirilux Poompradub Shinzo Kohjiya Yuko Ikeda 《Journal of Polymer Science.Polymer Physics》2004,42(6):956-964
The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004 相似文献
4.
5.
6.
Terahertz time-domain spectroscopy (THz-TDS) is used to study the intra- and intermolecular vibrational modes of aromatic carboxylic acids, for example, o-phthalic acid, benzoic acid, and salicylic acid, which form either intra- or intermolecular hydrogen bond(s) in different ways. Incorporating the target molecules in nano-sized spaces in mesoporous silicate (SBA-16) is found to be effective for the separate detection of intramolecular hydrogen bonding modes and intermolecular modes. The results are supported by an analysis of the differences in the peak shifts, which depend on temperature, caused by the different nature of the THz absorption. Raman spectra revealed that incorporating the molecules in the nano-sized pores of SBA-16 slightly changes the molecular structures. In the future, THz-TDS using nanoporous materials will be used to analyze the intra- and intermolecular vibrational modes of molecules with larger hydrogen bonding networks such as proteins or DNA. 相似文献
7.
Precise characterization of noncollinear optical parametric amplifier idler pulses that have bandwidths of more than an octave with a center wavelength at 990 nm was demonstrated. The method employed was cross-correlation frequency-resolved optical gating with broadband sum-frequency mixing to take advantage of the idler's angular dispersion. Compression to near the transform limit was achieved to produce quasi-monocyclic near-infrared pulses by use of a deformable membrane mirror. 相似文献
8.
Kai Kamada Shintaro Udo Shuichi Yamashita Yuko Tsutsumi Yasumichi Matsumoto 《Solid State Ionics》2003,160(3-4):389-394
Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al2O3 (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al2O3 and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi2Sr2CaCu2Oy (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm−2). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm−2). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount. 相似文献
9.
John A. Mikroyannidis Larysa Fenenko Masayuki Yahiro Chihaya Adachi 《Journal of polymer science. Part A, Polymer chemistry》2007,45(20):4661-4670
Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with ηEL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007 相似文献
10.
Takafumi Adachi Ichimin Shirotani Junichi Hayashi Osamu Shimomura 《Physics letters. A》1998,250(4-6):389-393
Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms. 相似文献