全文获取类型
收费全文 | 479篇 |
免费 | 20篇 |
国内免费 | 1篇 |
专业分类
化学 | 327篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 126篇 |
无线电 | 32篇 |
出版年
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2016年 | 2篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 15篇 |
2012年 | 17篇 |
2011年 | 16篇 |
2010年 | 14篇 |
2009年 | 22篇 |
2008年 | 19篇 |
2007年 | 16篇 |
2006年 | 22篇 |
2005年 | 15篇 |
2004年 | 17篇 |
2003年 | 27篇 |
2002年 | 9篇 |
2001年 | 11篇 |
2000年 | 10篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 13篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 12篇 |
1985年 | 20篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 15篇 |
1980年 | 17篇 |
1979年 | 10篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 7篇 |
1972年 | 3篇 |
1969年 | 2篇 |
1968年 | 3篇 |
排序方式: 共有500条查询结果,搜索用时 820 毫秒
91.
92.
Junko Hirota Dr. Kazuteru Usui Dr. Yasufumi Fuchi Masaomi Sakuma Shota Matsumoto Ryusuke Hagihara Prof. Dr. Satoru Karasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(65):14943-14952
Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines. 相似文献
93.
94.
Reflection spectra of silicate glasses were measured in the spectral region 2–13 eV. The bands due to bridging oxygen were found at 11.6 and 10.4–9.5 eV. The bands for non-bridging oxygens were found in the region 8.8–4.9 eV. They shift to lower energy with increasing ionic radius for the low valency cations while they shift to higher energy with increasing ionic radius for the high valency cations. The correlation between the measured bands and the absorption wavelength calculated from Drude-Voigt dispersion formula is discussed. 相似文献
95.
T. Kimura T. Sato M. Hirota S. Takagi 《Journal of Thermal Analysis and Calorimetry》2008,92(2):381-389
Excess enthalpies of sixteen binary mixtures between one each of methyl methylthiomethyl sulfoxide (MMTSO) and dimethyl sulfoxide
(DMSO) and one of ketone {CH3CO(CH2)nCH3, n=0 to 6 and CH3COC6H5} have been determined at 298.15 K. All the mixtures showed positive excess enthalpies over the whole range of mole fractions.
Excess enthalpies of ketone+MMTSO or DMSO increased with increasing the number of methylene radicals in the methyl alkyl ketone
molecules. Excess enthalpies of MMTSO+ketone are smaller than those of DMSO+ketone for the same ketone mixtures. The limiting
excess partial molar enthalpies of the ketone, H
1
E,∞, in all the mixtures with MMTSO were smaller than those of DMSO. Linear relationships were obtained between limiting excess
partial molar enthalpies and the number of methylene groups except 2-propanone. 相似文献
96.
Fujii T Yamaguchi S Hirota S Masuda H 《Dalton transactions (Cambridge, England : 2003)》2008,(1):164-170
Hydrogen atom abstraction reactions have been implicated in oxygenation reactions catalyzed by copper monooxygenases such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (DbetaM). We have investigated mononuclear copper(I) and copper(II) complexes with bis[(6-neopentylamino-2-pyridyl)methyl][(2-pyridyl)methyl]amine (BNPA) as functional models for these enzymes. The reaction of [Cu(II)(bnpa)]2+ with H2O2, affords a quasi-stable mononuclear copper(II)-hydroperoxo complex, [Cu(II)(bnpa)(OOH)]+ (4) which is stabilized by hydrophobic interactions and hydrogen bonds in the vicinity of the copper(II) ion. On the other hand, the reaction of [Cu(I)(bnpa)]+ (1) with O2 generates a trans-mu-1,2-peroxo dicopper(II) complex [Cu(II)2(bnpa)2(O2(2-]2+ (2). Interestingly, the same reactions carried out in the presence of exogenous substrates such as TEMPO-H, produce a mononuclear copper(II)-hydroperoxo complex 4. Under these conditions, the H-atom abstraction reaction proceeds via the mononuclear copper(II)-superoxo intermediate [Cu(II)(bnpa)(O2-)]+ (3), as confirmed from indirect observations using a spin trap reagent. Reactions with several substrates having different bond dissociation energies (BDE) indicate that, under our experimental conditions the H-atom abstraction reaction proceeds for substrates with a weak X-H bond (BDE < 72.6 kcal mol(-1)). These investigations indicate that the copper(II)-hydroperoxo complex is a useful tool for elucidation of H-atom abstraction reaction mechanisms for exogenous substrates. The useful functionality of the complex has been achieved via careful control of experimental conditions and the choice of appropriate ligands for the complex. 相似文献
97.
Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation
Akiharu Ueki Masafumi Hirota Keiko Komatsu Yutaka Takano Michio Iwaoka Hironobu Hojo Yoshiaki Nakahara 《Tetrahedron》2008,64(11):2611-2618
β-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf2O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner. 相似文献
98.
Hasegawa T Iijima K Hirota K Nakajima T Makino K Terada H 《Colloids and surfaces. B, Biointerfaces》2008,63(2):209-216
A method for exact determination of phagocytic activity of alveolar macrophage (M) cells toward synthetic microspheres (MS) by optical microscopy was developed. We examined the effectiveness of the treatment of M samples with trypsin, acid or xylene to remove the polystyrene latex microspheres (PSL MS) attached to M cell membranes during their phagocytosis by M cells. We found that centrifugation, which was employed to collect M samples after incubation with MS, affected significantly the efficiency of the various treatments. Of the three treatments, xylene treatment without centrifugation was the most effective to determine the phagocytic activity of M cells, as xylene dissolved the PSL MS on the cell surface almost completely. This treatment was also effective in the case of poly(lactic-co-glycolic acid) MS (PLGA MS), which have been commonly used as an efficient vehicle for drug delivery system. 相似文献
99.
100.
Copper(II) ion-bound CysGly dipeptides linked by an azobenzene derivative were photoisomerized between the trans and cis forms. The two copper(II) ion centers were positioned close to each other in the cis form, whereas they were far away from each other in the trans form. The copper complex in the cis form exhibited DNA cleavage activity, whereas the activity in the trans form was negligible. The DNA cleavage activity of the cis form is attributed to the cooperation of the closely located copper(II) centers. The present results show the photocontrol of the cooperation of metal ions for DNA cleavage. 相似文献