全文获取类型
收费全文 | 843篇 |
免费 | 29篇 |
国内免费 | 6篇 |
专业分类
化学 | 652篇 |
晶体学 | 5篇 |
力学 | 27篇 |
数学 | 31篇 |
物理学 | 163篇 |
出版年
2023年 | 9篇 |
2022年 | 9篇 |
2021年 | 18篇 |
2020年 | 32篇 |
2019年 | 32篇 |
2018年 | 9篇 |
2017年 | 12篇 |
2016年 | 22篇 |
2015年 | 18篇 |
2014年 | 25篇 |
2013年 | 35篇 |
2012年 | 49篇 |
2011年 | 53篇 |
2010年 | 25篇 |
2009年 | 23篇 |
2008年 | 61篇 |
2007年 | 40篇 |
2006年 | 36篇 |
2005年 | 47篇 |
2004年 | 33篇 |
2003年 | 34篇 |
2002年 | 26篇 |
2001年 | 11篇 |
2000年 | 16篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 11篇 |
1974年 | 5篇 |
1973年 | 9篇 |
1972年 | 6篇 |
排序方式: 共有878条查询结果,搜索用时 15 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.
Takumi Watanabe Yuichiro Nishizawa Haruka Minato Dr. Chihong Song Prof. Dr. Kazuyoshi Murata Prof. Dr. Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8934-8938
The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications. 相似文献
3.
Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described. 相似文献
4.
This paper reports a successful achievement of laser-induced biological cell fusion using an excimer laser excited dye laser. To our knowledge, we examined for the first time the dependence of fusion rate on laser pulse energy, number of laser pulses, and laser wavelength. Maximum fusion rate of approximately 50% was obtained by this laser fusion technology. 相似文献
5.
A new method for rotation and brightness invariant pattern recognition was proposed by applying multiple circular harmonic expansions to the joint transform correlator. The amplitudes of the multiple orders of circular harmonic expansions made from a detecting image were synthetically modified to respond to the same auto-correlation peaks. These modified circular harmonic expansions were arranged in the input plane as reference patterns together with an arbitrary target pattern, and the correlation signals between them were calculated in the subtracted joint transform correlator. The fraction of the correlation-peak intensities between the target and the references were extracted as a new discrimination parameter. This new parameter performs pattern recognition under rotation and brightness invariance with good discriminability. Its high discriminability has been proved in computer simulations using the face image patterns of many individuals. 相似文献
6.
The educational system has gradually shifted from a face-to-face to an e-learning system, which has become prevalent in advanced countries with the advance of information technology, and connection of global networks. Accordingly, a growing demand is emerging for more reliable individual certification with technical precision in order to measure and record learning achievements and credentials of participants. The present system has a limit in terms of registration capacity, therefore, its accuracy has often been questioned. Against this background, an individual certification system is proposed particularly for access control in e-learning. Under our proposed system, a compact optical correlator for facial recognition is employed. This correlator was previously tested for of biometrics authentication accuracy and proved highly reliable, having recorded remarkably low error rates (below 1%). The recorded error rate is sufficiently robust that the system itself can be regarded as a valid and practical viable attestation system. 相似文献
7.
Toshiaki Asakai Ryota Minegishi Norie Inaba Yutaka Ishimura Mariko Murayama Tatsuhiko Tanaka 《Analytical sciences》2006,22(3):461-463
The drying conditions for primary standards of volumetric analysis have a significant effect on the titration results due to changes in the purity, stability and homogeneity. Amidosulfuric acid, a strong acid used as a reference material for volumetric analysis in Japan, was dried in a vacuum desiccator or heated at different temperatures, and then measured by Karl-Fischer titration, thermogravimetry/mass spectroscopy (TG-MS), ion chromatography and coulometric titration. The optimum drying conditions were at 50 degrees C for 24 h with crushing. 相似文献
8.
J.D. Dutson D. Litvinov M.R.J. Gibbs Y. Inaba H. Muraoka K. O’Grady 《Journal of magnetism and magnetic materials》2006
In this paper, we discuss two key aspects of magnetisation reversal in magnetic thin films with perpendicular anisotropy. Firstly, a study has been made of the additional field required to erase data written perpendicular to a thin film recording disk as the linear data density is increased. It has been found that an increase in data density from 40 to 360 kfci results in an increase of 1.25 kOe in the field required to erase the data. Secondly, the effect of varying the level of exchange coupling by co-sputtering CoCrPt samples with SiO2 has been studied using a characterisation technique that is independent of the self-demagnetising field. It has been found that the samples are fully exchange de-coupled when the film contains >9.8% SiO2 and the activation volume of reversal remains constant for higher levels of SiO2. 相似文献
9.
Iwao Ojima Shin-Ichi Inaba Tetsuo Kogure Makoto Matsumoto Hideyuki Matsumoto Hamao Watanabe Yoichiro Nagai 《Journal of organometallic chemistry》1973,55(1):C4-C6
[RhCl(PPh3)3] is a very effective catalyst for the cleavage of Si-Si bonds by alcohols. 相似文献
10.
Masahiro?Okada Takumi?Matoba Masayoshi?OkuboEmail author 《Colloid and polymer science》2003,282(2):193-197
The influence of nonionic emulsifier, included inside styrene-methacrylic acid copolymer [P(S-MAA)] particles during emulsion copolymerization, on the formation of multihollow structure inside the particles via the alkali/cooling method (proposed by the authors) was examined in comparison to emulsifier-free particles. It was clarified that the nonionic emulsifier included inside the P(S-MAA) particles eased the formation of multihollow structure.Part CCL of the series studies on suspension and emulsion 相似文献