全文获取类型
收费全文 | 674篇 |
免费 | 10篇 |
国内免费 | 3篇 |
专业分类
化学 | 558篇 |
晶体学 | 2篇 |
力学 | 2篇 |
数学 | 34篇 |
物理学 | 91篇 |
出版年
2022年 | 6篇 |
2021年 | 5篇 |
2020年 | 10篇 |
2019年 | 8篇 |
2017年 | 3篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 21篇 |
2013年 | 25篇 |
2012年 | 35篇 |
2011年 | 43篇 |
2010年 | 26篇 |
2009年 | 19篇 |
2008年 | 42篇 |
2007年 | 42篇 |
2006年 | 47篇 |
2005年 | 37篇 |
2004年 | 42篇 |
2003年 | 48篇 |
2002年 | 46篇 |
2001年 | 13篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 9篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 11篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1985年 | 8篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 5篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有687条查询结果,搜索用时 15 毫秒
111.
Reductive amination reaction using 7-amino-4-methylcoumarin (AMC) as a fluorescent probe enabled analyses of glycoproteins' monosaccharides and N-linked oligosaccharides. Reductive amination of N-acetylhexosamines and AMC using sodium cyanoborohydride or dimethylamine-borane complex indicated slight recovery of derivatives, but pyridine-borane achieved better recoveries. Reversed-phase high-performance liquid chromatography (HPLC) analyses of monosaccharides constituting glycoprotein glycans using fluorimetric detection revealed linearity for 0.2fmol to 1pmol, with less than 5% RSD quantitation reproducibility. Reversed-phase HPLC analyses of glycoprotein glycans, combined with negative-ion electrospray ionization mass spectrometry (LC-ESI-MS), enabled their structural determination. Using this highly hydrophobic reagent, AMC-labeled oligosaccharides displayed one-order to two-order higher ESI-MS intensity than derivatives labeled using other reagents. 相似文献
112.
Zhang R Seki A Ishizone T Yokoyama H 《Langmuir : the ACS journal of surfaces and colloids》2008,24(10):5527-5533
Reduction of hydrophobic interaction in water is important in biological interfaces. In our previous work, we have found that poly(styrene- b-triethylene glycol methyl ether methacrylate) (PS-PME3MA) segregates the PME3MA block to the surface in hydrophobic environment, such as in air or in a vacuum, and shows remarkable resistance against adsorption or adhesion of proteins, platelets, and cells in water. In this paper, we report that atomic force microscopy (AFM) with hydrophobic probes can directly monitor the reduced hydrophobic interaction of the PS surfaces modified by poly(styrene- b-origoethylene glycol methyl ether methacrylate) (PS-PME NMA), where N is the number of ethylene glycol units. The pull-off forces between the hydrophobic probes that are coated with octyltrichlorosilane (OLTS) and the PS-PME NMA modified polystyrene (PS) surfaces in water were measured. The absolute spring constants and tip-curvatures of the AFM cantilevers were measured to compute the work of adhesion by the Johnson, Kendall, and Roberts (JKR) theory, which relates the pull-off force at which the separation occurs between a hemisphere and a plane to the work of adhesion. The hydrophobic interactions between the hydrophobic tip and polymer surfaces in water were greatly reduced with the segregated PME NMA blocks. The hydrophobic interactions decrease with increasing N of the series of PS-PME NMA and show a correlation with the amount of protein adsorbed. 相似文献
113.
Machida S Usuba K Blaskovich MA Yano A Harada K Sebti SM Kato N Ohkanda J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(5):1392-1401
Synthetic chemical probes designed to simultaneously targeting multiple sites of protein surfaces are of interest owing to their potential application as site specific modulators of protein-protein interactions. A new approach toward bivalent inhibitors of mammalian type I geranylgeranyltransferase (GGTase I) based on module assembly for simultaneous recognition of both interior and exterior protein surfaces is reported. The inhibitors synthesized in this study consist of two modules linked by an alkyl spacer; one is the tetrapeptide CVIL module for binding to the interior protein surface (active pocket) and the other is a 3,4,5-alkoxy substituted benzoyl motif that contains three aminoalkyl groups designed to bind to the negatively charged protein exterior surface near the active site. The compounds were screened by two distinct enzyme inhibition assays based on fluorescence spectroscopy and incorporation of a [(3)H]-labeled prenyl group onto a protein substrate. The bivalent inhibitors block GGTase I enzymatic activity with K(i) values in the submicromolar range and are approximately one order of magnitude and more than 150 times more effective than the tetrapeptide CVIL and the methyl benzoate derivatives, respectively. The bivalent compounds 6 and 8 were shown to be competitive inhibitors, suggesting that the CVIL module anchors the whole molecule to the GGTase I active site and delivers the other module to the targeting protein surface. Thus, our module-assembly approach resulted in simultaneous multiple-site recognition, and as a consequence, synergetic inhibition of GGTase I activity, thereby providing a new approach in designing protein-surface-directed inhibitors for targeting protein-protein interactions. 相似文献
114.
Inagaki K Narukawa T Yarita T Takatsu A Okamoto K Chiba K 《Analytical and bioanalytical chemistry》2007,389(3):691-696
A coprecipitation method using sample constituents as carrier precipitants was developed that can remove molybdenum, which
interferes with the determination of cadmium in grain samples via isotope dilution inductively coupled plasma mass spectrometry
(ID-ICPMS). Samples were digested with HNO3, HF, and HClO4, and then purified 6 M sodium hydroxide solution was added to generate colloidal hydrolysis compounds, mainly magnesium hydroxide.
Cadmium can be effectively separated from molybdenum because the cadmium forms hydroxides and adsorbs onto and/or is occluded
in the colloid, while the molybdenum does not form hydroxides or adsorb onto the hydrolysis colloid. The colloid was separated
by centrifugation and then dissolved with 0.2 M HNO3 solution to recover the cadmium. The recovery of Cd achieved using the coprecipitation was >97%, and the removal efficiency
of Mo was approximately 99.9%. An extremely low procedural blank (below the detection limit of ICPMS) was achieved by purifying
the 6 M sodium hydroxide solution via Mg coprecipitation using Mg(NO3)2 solution. The proposed method was applied to two certified reference materials (NIST SRM 1567a wheat flour and SRM 1568a
rice flour) and CCQM-P64 soybean powder. Good analytical results with small uncertainties were obtained for all samples. This
method is simple and reliable for the determination of Cd in grain samples by ID-ICPMS.
Figure Overview of a coprecipitation method using sample constituents 相似文献
115.
Fujiwara A Kameo Y Hoshi A Haraga T Nakashima M 《Journal of chromatography. A》2007,1140(1-2):163-167
Extraction chromatography with commercially available UTEVA resin (for uranium and tetravalent actinide) was applied for the separation of Th and U from control solutions prepared from a multi-element control solution and from sample solutions of solidified simulated waste. Thorium and U in control solutions with 1-5mol/dm(3) HNO(3) were extracted with UTEVA resin and recovered with a solution containing 0.1mol/dm(3) HNO(3) and 0.05mol/dm(3) oxalic acid to be separated from the other metallic elements. Extraction behavior of U in the sample solutions was similar to that in the control solutions, but extraction of Th was dependent on the concentration of HNO(3). Thorium was extracted from 5mol/dm(3) HNO(3) sample solutions but not from 1mol/dm(3) HNO(3) sample solutions. We conjecture that thorium fluoride formation interferes with extraction of Th. Addition of Al(NO(3))(3) and Fe(NO(3))(3), which have higher stability constant with fluoride ion than Th, does improve extractability of Th from 1mol/dm(3) HNO(3) sample solution. 相似文献
116.
Kanai T Sawada T Toyotama A Yamanaka J Kitamura K 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3503-3505
The optical stop band in colloidal crystals is characterized by the central frequency and bandwidth. Although the former is known to be highly tunable by changing the lattice constant, the latter is basically determined by the refractive index contrast between the particles and the background medium that is intrinsic to the materials. In this study, we show that the effective bandwidth in gelled colloidal crystals can also be tuned by controlling the fabrication conditions. Single-domain gelled colloidal crystals were prepared by photopolymerization under various photoirradiation conditions. It was observed that the width of the stop band in the transmission or reflectance spectrum could be expanded by simply adjusting the irradiation time. 相似文献
117.
Kouki Ikuta Tsutomu Kudo Noboru Yoshikane Nilesh J. Vasa Yuji Oki Mitsuo Maeda 《Optical Review》1999,6(5):464-470
Improvement of an infrared light detection and ranging (IR-lidar) system for a short range (0–1000 m) and with high resolution is studied to enhance a geometrical form factor. Theoretical modeling of Mie scattering echo signals agrees with the experimental results. Introduction of a lens in front of the detector is effective for increasing the geometrical form factor, and a significant improvement in the received signal intensity is achieved, especially for short-range measurements around 100 m. This is useful for the IR-lidar system with a detector diameter of less than 1 mm. In the theoretical model, a ray-tracing technique was applied and a transmitting laser beam with Gaussian profile was considered for better accuracy. 相似文献
118.
119.
120.
Kensuke Naka Akiko Kobayashi Yoshiki Chujo 《Macromolecular rapid communications》1997,18(12):1025-1032
The star-shaped polymer with trans-tetrapyridyl complex of Ru(II) as a core was prepared by complexation of ester-linked pyridyl-terminated poly(oxyethylene) (M̄n = 2000) with a Ru5Cl122− cluster. The unimodal peak of the star-shaped polymer in the gel-permeation chromatogram was shifted to a higher molecular weight region than that of the starting prepolymer. The electron-withdrawing ester substituent in para position of the pyridine ring shifted the metal-to-ligand charge transfer (MLCT) band into the visible region. 相似文献