全文获取类型
收费全文 | 1817篇 |
免费 | 40篇 |
国内免费 | 12篇 |
专业分类
化学 | 1263篇 |
晶体学 | 26篇 |
力学 | 29篇 |
数学 | 97篇 |
物理学 | 454篇 |
出版年
2023年 | 8篇 |
2022年 | 12篇 |
2021年 | 21篇 |
2020年 | 19篇 |
2019年 | 17篇 |
2018年 | 17篇 |
2016年 | 38篇 |
2015年 | 27篇 |
2014年 | 27篇 |
2013年 | 84篇 |
2012年 | 86篇 |
2011年 | 104篇 |
2010年 | 56篇 |
2009年 | 55篇 |
2008年 | 93篇 |
2007年 | 119篇 |
2006年 | 125篇 |
2005年 | 138篇 |
2004年 | 107篇 |
2003年 | 94篇 |
2002年 | 99篇 |
2001年 | 39篇 |
2000年 | 33篇 |
1999年 | 29篇 |
1998年 | 14篇 |
1997年 | 15篇 |
1996年 | 15篇 |
1995年 | 23篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 13篇 |
1991年 | 14篇 |
1990年 | 18篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 20篇 |
1985年 | 19篇 |
1984年 | 21篇 |
1983年 | 11篇 |
1982年 | 16篇 |
1981年 | 20篇 |
1980年 | 19篇 |
1979年 | 19篇 |
1978年 | 11篇 |
1977年 | 14篇 |
1975年 | 12篇 |
1974年 | 14篇 |
1968年 | 7篇 |
1967年 | 8篇 |
排序方式: 共有1869条查询结果,搜索用时 15 毫秒
951.
Hiromu Kawakubo Tomoko Suzuki Kazutaka Nishino Futaba Hara Tomoyoshi Takano Yoshito Takebayashi 《合成通讯》2013,43(9):1068-1072
Diethyl azodicarboxylate (DEAD) is a well-known coupling reagent that can be readily synthesized from diethylhydrazodicarboxylate (DEHD). The bromination of commercially available ethyl allophanate (1) in CHCl3, followed by the Hofmann-type rearrangement reaction of the resulting N-brominated species 2 and 3 in C2H5OH in the presence of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), gave DEHD in good yield from a one-pot process. Interestingly, however, the bromination and Hofmann-type rearrangement reactions did not occur in the presence of N(C2H5)3. These results therefore suggest that this reaction is reliant upon a high level of reactivity during the bromination reaction to give 2 and 3, and that these N-brominated species require the presence of a strong and nonnucleophilic base to undergo the Hofmann-type rearrangement to give DEHD. 相似文献
952.
Zhanying Zhang Ian M. O’Hara William O. S. Doherty 《Cellulose (London, England)》2013,20(6):3179-3190
Pretreatments of sugarcane bagasse by three high boiling-point polyol solutions were compared in acid-catalysed processes. Pretreatments by ethylene glycol (EG) and propylene glycol solutions containing 1.2 % H2SO4 and 10 % water at 130 °C for 30 min removed 89 % lignin from bagasse resulting in a glucan digestibility of 95 % with a cellulase loading of ~20 FPU/g glucan. Pretreatment by glycerol solution under the same conditions removed 57 % lignin with a glucan digestibility of 77 %. Further investigations with EG solutions showed that increases in acid content, pretreatment temperature and time, and decrease in water content improved pretreatment effectiveness. A good linear correlation of glucan digestibility with delignification was observed with R2 = 0.984. Bagasse samples pretreated with EG solutions were characterised by scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction, which confirmed that improved glucan enzymatic digestibility is mainly due to delignification and defibrillation of bagasse. Pretreatment by acidified EG solutions likely led to the formation of EG-glycosides. Up to 36 % of the total lignin was recovered from pretreatment hydrolysate, which may improve the pretreatment efficiency of recycled EG solution. 相似文献
953.
Traces of zinc, lead, copper and cadmium are determined simultaneously by anodic-stripping voltammetry (ASV) combined with a preconcentration technique utilizing C(18)-bonded glass beads. The metals are collected as their 2-(2-pyridylazo)-5-diethylaminophenol (PADAP) complexes on a column of the beads and the complexes are eluted with a small volume of ethanol-hydrochloric acidchloroform mixture. The eluate is evaporated to dryness in the presence of hydrogen peroxide and the residue dissolved in a small volume of acetic acid-sodium acetate buffer. The concentrations of the metals are measured by ASV, Quantitative recoveries are obtained for 0.01-ng ml levels of the metals. Many ions which interfere in the direct ASV procedure do not interfere in the present method. 相似文献
954.
Ikuyoshi Tomita Masanori Taguchi Koji Takagi Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1997,35(3):431-437
A living block copolymerization of allene derivatives with 1-phenylethyl isocyanide ( 3 ) using [(allyl)NiOCOCF3]2 ( 1 ) is described. After complete polymerization of allene monomers such as n-octyloxyallene ( 2A ) with 1 , further addition of 3 to the reaction system yielded the corresponding block copolymers in high yield. For instance, a block copolymer ( 4A , Mn = 39,600, Mw/Mn = 1.20) was obtained in 96% yield by the addition of 3 ([ 3 ]/[ 1 ] = 250) to the living solution of poly(n-octyloxyallene) (Mn = 14,400, Mw/Mn = 1.03) prepared by the polymerization of 2A in the ratio of [ 2A ]/[ 1 ] = 90. The resulting copolymer was a brownish orange gum or a solid, depending on the length of each of the segments. The solubility of the block copolymers could be controlled by the allene components. The copolymer of 2A with 3 having appropriate length of segments was soluble in n-hexane, while that of methoxyethoxyethoxyallene ( 2D ) with 3 was soluble in methanol. © 1997 John Wiley & Sons, Inc. 相似文献
955.
A novel class of microstructured optical fiber coupler is introduced that operates by resonant, rather than proximity, energy transfer by means of transverse light guides built into a fiber cross section. Such a design permits significant spatial separation between interacting fibers, which, in turn, eliminates intercore cross talk owing to proximity coupling. A controllable energy transfer between the cores is then achieved by localized and highly directional transmission through a transverse light guide. The main advantage of this coupling scheme is its inherent scalability, as one can integrate additional fiber cores into the existing fiber cross section simply by placing the cores far enough from the existing optical circuitry to prevent proximity cross talk and then making the necessary intercore connections with transverse light wires, in direct analogy with on-chip electronics integration. 相似文献
956.
Kidera M Takahashi K Enomoto S Mitsubori Y Goto A Yano Y 《European journal of mass spectrometry (Chichester, England)》2007,13(4):239-248
The ionization efficiency of an electron cyclotron resonance ion source (ECRIS) is generally high, and all elements can be fundamentally ionized by the high-temperature plasma. We focused our attention on the high potentiality of ECRIS as an ion source for mass spectrometers and attempted to customize the mass spectrometer equipped with an ECRIS. Precise measurements were performed by using an ECRIS that was specialized and customized for elemental analysis. By using the charge-state distribution and the isotope ratio, the problem of overlap such as that observed in the spectra of isobars could be solved without any significant improvement in the mass resolution. When the isotope anomaly (or serious mass discrimination effect) was not observed in ECR plasma, the system was found to be very effective for isotope analysis. In this paper, based on the spectrum (ion current as a function of an analyzing magnet current) results of low charged state distributions (2+, 3+, 4+, ...) of noble gases, we discuss the feasibility of an elemental analysis system employing an ECRIS, particularly for isotopic analysis. The high-performance isotopic analysis obtained for ECRIS mass spectrometer in this study suggests that it can be widely applied to several fields of scientific study that require elemental or isotopic analyses with high sensitivity. 相似文献
957.
Specificity of acyl transfer from 2-mercaptobenzamide thioesters to the HIV-1 nucleocapsid protein 总被引:1,自引:0,他引:1
Miller Jenkins LM Hara T Durell SR Hayashi R Inman JK Piquemal JP Gresh N Appella E 《Journal of the American Chemical Society》2007,129(36):11067-11078
The HIV-1 nucleocapsid protein (NCp7) is a small, highly conserved protein with two zinc-binding domains that are essential for the protein's function. Molecules that bind to and inactivate NCp7 are currently being evaluated as new antiviral drugs. In particular, derivatives based on a 2-mercaptobenzamide thioester template have been shown to specifically eject zinc from the C-terminal zinc-binding domain (ZD2) of NCp7 via acyl transfer from the thioester to a cysteine sulfur. In this study, mutational analysis of the NCp7 amino acid sequence has been used to investigate the specificity of the interaction between ZD2 and a 2-mercaptobenzamide thioester compound using UV-vis spectroscopy and mass spectrometry to monitor the rate of metal ejection from NCp7 mutant peptides and sites of acylation, respectively. We were able to extend the previously reported mechanism of action of these thioester compounds to include a secondary S to N intramolecular acyl transfer that occurs after the primary acyl transfer from the thioester to a cysteine side chain in the protein. Structural models of the thioester/ZD2 complex were then examined to identify the most likely binding orientation. We determined that position x+1 (where x is Cys36) needs to be an aromatic residue for reactivity and a hydrogen-bond donor in position x+9 is important for optimal reactivity. A basic residue (lysine or arginine) is required at position x+2 for the correct fold, while a lysine residue is needed for reactivity involving S to N acyl transfer. We report highly specific interactions between 2-mercaptobenzamide thioester compounds and NCp7 that offer a structural basis for refining and designing new antiretroviral therapeutics, directed toward a target that is resistant to viral mutation. 相似文献
958.
Stepan Stehlik Tomas Kohoutek Miloslav Frumar Toru Hara Kazuyuki Ueda 《Journal of solid state chemistry》2010,183(1):144-149
This article describes the preparation of multi-walled carbon nanotube—chalcogenide glass composite by direct synthesis and the melt-quenching method. The carbon nanotubes—chalcogenide glass composite was characterized by high-resolution transmission electron microscopy (HRTEM), TEM/energy-dispersive X-ray spectroscopy, low energy electron excited X-ray spectroscopy, Raman spectroscopy, spectroscopic ellipsometry, microhardness, and impedance spectroscopy. CNTs-AgAsS2 glass composite possess highly increased ionic conductivity, from σ25 °C=4.38±0.0438×10−6 to σ25 °C=6.57±0.0657×10−6 S cm−1 and decreased refractive index from n=2.652 to 2.631 at the wavelength λ=1.55 μm. 相似文献
959.
Dr. Patrick Commins Dr. Hideyuki Hara Prof. Panče Naumov 《Angewandte Chemie (International ed. in English)》2016,55(42):13028-13032
One of the most inevitable limitations of any material that is exposed to mechanical impact is that they are inexorably prone to mechanical damage, such as cracking, denting, gouging, or wearing. To confront this challenge, the field of polymers has developed materials that are capable of autonomous self‐healing and recover their macroscopic integrity similar to biological organisms. However, the study of this phenomenon has mostly remained within the soft materials community and has not been explored by solid‐state organic chemists. The first evidence of self‐healing in a molecular crystal is now presented using crystals of dipyrazolethiuram disulfide. The crystals were mildly compressed and the degree of healing was found to be 6.7 %. These findings show that the self‐healing properties can be extended beyond mesophasic materials and applied towards the realm of ordered solid‐state compounds. 相似文献
960.
Nickel-catalyzed three-component coupling of bis-1,3-dienes, aldehyde, and dimethylzinc was investigated. In the presence of catalytic amounts of Ni(acac)2 and PPh3, bis-1,3-dienes smoothly react with an aldehyde and dimethylzinc via intramolecular cyclodimerization of bis-1,3-diene moiety. The reaction proceeds through formation of a cyclic bis-allylnickel complex, insertion of an aldehyde, and addition of dimethylzinc to the resulting oxanickellacycle intermediate. An enantioselective coupling was also achieved by the use of a chiral monodentate phosphine ligand, H-MOP. 相似文献