全文获取类型
收费全文 | 742篇 |
免费 | 30篇 |
国内免费 | 4篇 |
专业分类
化学 | 614篇 |
晶体学 | 6篇 |
力学 | 2篇 |
数学 | 44篇 |
物理学 | 110篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 11篇 |
2020年 | 18篇 |
2019年 | 15篇 |
2018年 | 15篇 |
2017年 | 11篇 |
2016年 | 20篇 |
2015年 | 25篇 |
2014年 | 24篇 |
2013年 | 23篇 |
2012年 | 62篇 |
2011年 | 65篇 |
2010年 | 18篇 |
2009年 | 27篇 |
2008年 | 50篇 |
2007年 | 45篇 |
2006年 | 47篇 |
2005年 | 44篇 |
2004年 | 34篇 |
2003年 | 30篇 |
2002年 | 24篇 |
2001年 | 21篇 |
2000年 | 6篇 |
1999年 | 10篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1985年 | 7篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1968年 | 3篇 |
1963年 | 2篇 |
1961年 | 3篇 |
1959年 | 2篇 |
排序方式: 共有776条查询结果,搜索用时 15 毫秒
61.
A ring-closing metathesis reaction of allenynes occurred at room temperature in the presence of a molybdenum alkylidene complex to give ring-closed vinylallenes. The vinylallene skeletons were constructed by a metathesis-type reaction between the alkyne moiety and the proximal carbon-carbon double bond of the allene moiety. [reaction: see text] 相似文献
62.
Fujikawa Y Nagao T Yamada-Takamura Y Sakurai T Hashimoto T Morikawa Y Terakura K Lagally MG 《Physical review letters》2005,94(8):086105
The structure and stability of the hydrogen-terminated (105) surface of Ge deposited on Si(105) substrates are investigated by scanning tunneling microscopy (STM). Investigations combining STM, electron energy loss spectroscopy, and theory reveal that Si incorporation into the surface Ge layer of hydrogen-terminated Ge/Si(105) drastically destabilizes the surface. The STM images obtained on this surface are well explained by the recently established rebonded-step structure model. 相似文献
63.
The photoinduced decarbonylation of a ruthenium(II) carbonyl octaethylporphyrin (RuOEP(CO)(Py)) complex has been shown to occur upon nanosecond pulse laser irradiation as a visible light excitation source, which is reasonably interpreted by a stepwise two-photon absorption process. 相似文献
64.
Hozumi N Yamashita R Lee CK Nagao M Kobayashi K Saijo Y Tanaka M Tanaka N Ohtsuki S 《Ultrasonics》2004,42(1-9):717-722
The authors have proposed a new type of ultrasonic microscopy for biological tissue characterization. The system is driven by a nanosecond pulse voltage, the generated acoustic wave being reflected at the front and rear side of the sliced tissue. In this report, a time-frequency analysis was applied to determine the sound speed thorough the tissue. Frequency dependence of sound speed was obtained with a myocardium of a rat sliced into 10 microm. As the reflected waveform had a significant amount of oscillating component, the waveform was once subjected to the deconvolution process. As the result, two reflections were clearly separated in time domain. Then these two reflections were separately analyzed by time-frequency analysis. Each reflection was extracted by using a proper window function. Phase angles of these reflections at the same frequency were compared. A sound speed micrograph at an arbitrary frequency in between 50 and 150 MHz was successfully obtained. A tendency was found that the sound speed slightly increases with frequency. 相似文献
65.
Kimura M Wada K Iwashima Y Ohta K Hanabusa K Shirai H Kobayashi N 《Chemical communications (Cambridge, England)》2003,(19):2504-2505
Sol-gel polymerization of tetraethoxysilane in the presence of amphiphilic phthalocyanine polymer 2 produced organic-inorganic composites with the rod-like phthalocaynine polymers incorporated within ordered hexagonal channels. 相似文献
66.
Kimura M Sakaguchi A Ohta K Hanabusa K Shirai H Kobayashi N 《Inorganic chemistry》2003,42(9):2821-2823
A new class of sterically hindered phthalocyanine has been synthesized and characterized. Pentaphenylbenzene units were introduced at the periphery of each phthalocyanine to yield a sterically protected metal center. The attachment of the bulky oligophenylbenzene units resulted in the complete isolation of individual MPc molecules. The pockets around a cobalt center affect selectivity in the ligation of pyridines that have different sizes and shapes. 相似文献
67.
Mostafa Abdelrahman Sho Hirata Takuya Mukae Tomohiro Yamada Yuji Sawada Magdi El-Syaed Yutaka Yamada Muneo Sato Masami Yokota Hirai Masayoshi Shigyo 《Molecules (Basel, Switzerland)》2021,26(5)
Garlic (Allium sativum) is the second most important Allium crop that has been used as a vegetable and condiment from ancient times due to its characteristic flavor and taste. Although garlic is a sterile plant that reproduces vegetatively through cloves, garlic shows high biodiversity, as well as phenotypic plasticity and environmental adaptation capacity. To determine the possible mechanism underlying this phenomenon and to provide new genetic materials for the development of a novel garlic cultivar with useful agronomic traits, the metabolic profiles in the leaf tissue of 30 garlic accessions collected from different geographical regions, with a special focus on the Asian region, were investigated using LC/MS. In addition, the total saponin and fructan contents in the roots and cloves of the investigated garlic accessions were also evaluated. Total saponin and fructan contents did not separate the garlic accessions based on their geographical origin, implying that saponin and fructan contents were clone-specific and agroclimatic changes have affected the quantitative and qualitative levels of saponins in garlic over a long history of cultivation. Principal component analysis (PCA) and dendrogram clustering of the LC/MS-based metabolite profiling showed two major clusters. Specifically, many Japanese and Central Asia accessions were grouped in cluster I and showed high accumulations of flavonol glucosides, alliin, and methiin. On the other hand, garlic accessions grouped in cluster II exhibited a high accumulation of anthocyanin glucosides and amino acids. Although most of the accessions were not separated based on country of origin, the Central Asia accessions were clustered in one group, implying that these accessions exhibited distinct metabolic profiles. The present study provides useful information that can be used for germplasm selection and the development of new garlic varieties with beneficial biotic and abiotic stress-adaptive traits. 相似文献
68.
Mack J Bunya M Shimizu Y Uoyama H Komobuchi N Okujima T Uno H Ito S Stillman MJ Ono N Kobayashi N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(16):5001-5020
The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l]-21,23-dithia-, 5,10,15,20-tetraphenyltribenzo[g,q,l]-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids. 相似文献
69.
Yuta Tsunoda Katsunori Fukuta Taisuke Imamura Prof. Dr. Ryo Sekiya Dr. Taniyuki Furuyama Prof. Dr. Nagao Kobayashi Prof. Dr. Takeharu Haino 《Angewandte Chemie (International ed. in English)》2014,53(28):7243-7247
Encapsulation of chiral guests in the dissymmetric capsule 1?4 BF4 formed diastereomeric supramolecular complexes G ? 1?4 BF4 ( G : guest). When chiral guests 2 a – q were encapsulated within the dissymmetric space of the self‐assembled capsule 1?4 BF4, circular dichroism (CD) was observed at the absorption bands that are characteristic of the π–π* transition of the bipyridine moiety of the capsule, which suggests that the P and M helicities of the capsule are biased by the chiral guest complexation. The P helicity of diastereomeric complex (S)‐ 2 l ? 1?4 BF4 was determined to be predominant, based on CD exciton coupling theory and DFT calculations. The diastereoselectivity was highly influenced by the ester substituents, such that benzyl ester moieties were good for improving the diastereoselectivity. A diastereomeric excess of 98 % was achieved upon the complexation of 2 j . The relative enthalpic and entropic components for the distereoselectivity were obtained from a van’t Hoff plot. The enthalpic components were linearly correlated with the substituent Hammett parameters (σp+). The electron‐rich benzyl ester moieties generated donor–acceptor π–π stacking interactions with the bipyridine moiety, which resulted in a significant difference in energy between the predominant and subordinate diastereomeric complexes. 相似文献
70.
Zhang X Kobayashi N Jiang J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,64(2):526-531
Nuclear magnetic shielding tensors of porphine have been calculated at density functional B3LYP and PBE level using the gauge independent atomic orbital (GIAO) method. The geometries used were optimized using the 6-31G(d) basis set and the NMR calculations were performed using 6-31G(d) and 6-311G(d,p) basis sets, respectively. The calculated NMR shielding tensors and chemical shifts of porphine are compared with previous calculations as well as experimental data and satisfying results are obtained. Further NMR calculations are extended to metal-free and metallo-porphyrazine, -phthalocyanine, and -naphthalocyanine for the first time and the results are compared with experimental data available. The chemical shifts of the atoms in these compounds are assigned according to the experimental data available. 相似文献