全文获取类型
收费全文 | 1414篇 |
免费 | 49篇 |
国内免费 | 7篇 |
专业分类
化学 | 1144篇 |
晶体学 | 8篇 |
力学 | 17篇 |
数学 | 61篇 |
物理学 | 240篇 |
出版年
2023年 | 11篇 |
2022年 | 5篇 |
2021年 | 9篇 |
2020年 | 25篇 |
2019年 | 21篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 22篇 |
2015年 | 27篇 |
2014年 | 26篇 |
2013年 | 69篇 |
2012年 | 83篇 |
2011年 | 92篇 |
2010年 | 45篇 |
2009年 | 46篇 |
2008年 | 95篇 |
2007年 | 63篇 |
2006年 | 94篇 |
2005年 | 85篇 |
2004年 | 92篇 |
2003年 | 72篇 |
2002年 | 69篇 |
2001年 | 24篇 |
2000年 | 15篇 |
1999年 | 21篇 |
1998年 | 23篇 |
1997年 | 10篇 |
1996年 | 21篇 |
1995年 | 12篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 12篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 23篇 |
1984年 | 19篇 |
1983年 | 10篇 |
1982年 | 20篇 |
1981年 | 16篇 |
1980年 | 16篇 |
1979年 | 16篇 |
1978年 | 8篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 12篇 |
1974年 | 11篇 |
排序方式: 共有1470条查询结果,搜索用时 15 毫秒
51.
52.
Sakamoto S Ito A Kudo K Yoshikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(15):3717-3726
The introduction of a flavin chromophore on the myoglobin (Mb) surface and an effective electron-transfer (ET) reaction through the flavin were successfully achieved by utilizing the self-assembly of heterostranded coiled-coil peptides. We have prepared a semiartificial Mb, named Mb-1alphaK, in which an amphiphilic and cationic alpha-helix peptide is conjugated at the heme propionate (Heme-1alphaK). Heme-1alphaK has a covalently bound iron-protoporphyrin IX (heme) at the N terminus of a 1alphaK peptide sequence. This sequence was designed to form a heterostranded coiled-coil in the presence of a counterpart amphiphilic and anionic 1alphaE peptide sequence in a parallel orientation. Two peptides, Fla(1)-1alphaE and Fla(31)-1alphaE, both incorporating a 10-methylisoalloxazine moiety as an artificial flavin molecule, were also prepared (Fla=2-[7-(10-methyl)isoalloxazinyl]-2-oxoethyl). Heme-1alphaK was successfully inserted into apomyoglobin to give Mb-1alphaK. Mb-1alphaK recognized the flavin-modified peptides and a two-alpha-helix structure was formed. In addition, an efficient ET from reduced nicotinamide adenine dinucleotide to the heme center through the flavin unit was observed. The ET rate was faster in the presence of Fla(1)-1alphaE than in the presence of Fla(31)-1alphaE or the equivalent molecule that has no peptide chain. These results demonstrate that the introduction of a functional chromophore on the Mb surface can be achieved by using specific peptide-peptide interactions. Moreover, the dependence of the ET rate on the position of the flavin indicated that the distance between the heme active site and the flavin chromophore was regulated by the three-dimensional structure of the designed polypeptide. 相似文献
53.
Capillary zone electrophoresis was used for characterising nine samples of natural organic matter (NOM) using phosphate buffer (25 mM, pH 7) and various modifiers; methanol (50 mM), acetonitrile (10%,v/v), dimethyl sulfoxide (5%,v/v), and urea (5 M). Principal component analysis (PCA) was used to examine whether the electrophoretic profiles can be utilised as fingerprints for tracing the NOM samples to their source and/or type of location. It was found that all modifiers except methanol affect the electropherograms. Furthermore, it was found that the PCA analysis carried out on the electrophoretic profiles recorded in buffer solution modified by urea gave the best results for fingerprinting. The distribution of the fingerprints suggests a model for the humic substances in which all samples can be regarded as mixtures between two endmembers: autochtonous and allocthoneous NOM. 相似文献
54.
Ikehata J Shinomiya K Kobayashi K Ohshima H Kitanaka S Ito Y 《Journal of chromatography. A》2004,1025(2):169-175
The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems. 相似文献
55.
Belik AA Azuma M Matsuo A Whangbo MH Koo HJ Kikuchi J Kaji T Okubo S Ohta H Kindo K Takano M 《Inorganic chemistry》2005,44(19):6632-6640
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy. 相似文献
56.
Fukuji Higashi Michihide Ozawa Akihiko Mochizuki 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):637-643
The reaction promoted by diphenyl chlorophosphate (DPCP) in pyridine was successfully applied to the preparation of soluble aromatic copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, bisphenols, and a wide range of mol % aromatic diamines. Dropwise addition of a mixture of bisphenols and diamines (more favorably of bisphenols and then diamines) to the mixture of dicarboxylic acids activated by DPCP led the reactions homogeneously even with high mol % of diamines to produce copolymers of good solubility. This improved copolymer solubility was roughly estimated by sequence distribution of polyamide and polyester units in the copolymers, which was studied in a model reaction and in the copolycondensations by simultaneous and stepwise addition of bisphenols and diamines. 相似文献
57.
Ando M Takizawa M Suwabe S Yamato S Shimada K 《European journal of mass spectrometry (Chichester, England)》2003,9(6):619-622
Analysis of selenium in biological samples is very important and numerous analytical methods for the element have been developed. One of the most convenient and widely used methods for routine determination of serum selenium is a fluorometric method using 2,3-diaminonaphthalene (DAN); however, this method lacks specificity. We observed that 4,5-benzopiazselenol (BPS), a selenium derivative of DAN, is ionized with electron capture in an atmospheric pressure chemical ionization (APCI) interface, and subsequently established a method for determining total human serum selenium by means of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry. All pretreatment procedures were carried out in a single test tube to minimize selenium loss. The recovery of organic or inorganic selenium spiked to human serum was 97-103%.The detection limit of BPS was equivalent to 0.2 ng of selenium and the lower quantitative limit of serum selenium was 10 ng mL(-1). The coefficient of variation of standard concentrations in control serum samples was 4.5%. The purity of the observed peak obtained from serum samples was confirmed using the ion cluster technique. 相似文献
58.
The photoluminescence (PL) properties of ZrO2 have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO2 specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO2 film crystal on Zr ) and nanocrystals (surface area: 35–45m2/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O2 gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO2 nanocrystals. 相似文献
59.
The effect of metal ions on the conformation of thymine-containing poly-D-lysine was studied by CD spectra in aqueous solution. Of the metal ions studied, only copper(II) ion affected the conformation of nucleic acid analogs. Copper(II) ion also affected the specifically interacting system made up of thymine-containing poly-D-lysine and polyadenylic acid. 相似文献
60.
Susumu Takigawa Masanori Koshimizu Takio Noguchi Tsutomu Aida Seiichi Takami Tadafumi Adschiri Yutaka Fujimoto Akira Yoko Gimyeong Seong Takaaki Tomai Keisuke Asai 《Journal of Radioanalytical and Nuclear Chemistry》2017,314(2):611-615
We synthesized liquid scintillators incorporating ZrO2 nanoparticles for application in neutrinoless double beta decay experiments. ZrO2 nanoparticles of less than 10 nm in size were synthesized with sub- and supercritical hydrothermal methods. The Zr concentrations in the liquid scintillators were determined to be up to 1.4 wt% with inductively coupled plasma analysis, and the liquid scintillators were transparent to scintillation. These results indicate that these methods are applicable for the preparation of liquid scintillators for neutrinoless double beta decay experiments. 相似文献