全文获取类型
收费全文 | 1365篇 |
免费 | 64篇 |
国内免费 | 5篇 |
专业分类
化学 | 1059篇 |
晶体学 | 5篇 |
力学 | 37篇 |
数学 | 147篇 |
物理学 | 186篇 |
出版年
2024年 | 2篇 |
2023年 | 17篇 |
2022年 | 55篇 |
2021年 | 85篇 |
2020年 | 36篇 |
2019年 | 45篇 |
2018年 | 21篇 |
2017年 | 20篇 |
2016年 | 58篇 |
2015年 | 48篇 |
2014年 | 52篇 |
2013年 | 72篇 |
2012年 | 94篇 |
2011年 | 101篇 |
2010年 | 74篇 |
2009年 | 61篇 |
2008年 | 93篇 |
2007年 | 92篇 |
2006年 | 59篇 |
2005年 | 75篇 |
2004年 | 62篇 |
2003年 | 39篇 |
2002年 | 31篇 |
2001年 | 16篇 |
2000年 | 12篇 |
1999年 | 7篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1979年 | 5篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1973年 | 2篇 |
1966年 | 1篇 |
1921年 | 1篇 |
1887年 | 1篇 |
排序方式: 共有1434条查询结果,搜索用时 62 毫秒
31.
The catalytic (C/Pd) hydrogenation of 3-arylamino-2-nitro-2-enones ( 1 ) in the presence of carboxylic ortho esters ( 2 ) affords 4-acyl-1-arylimidazoles ( 3 ) in yields (20–70%) which depend on the degree of substitution of the imidazole ring. The spectral properties of compounds 3 , and particularly the 13C-nmr spectra, reflect both the electronic and steric effects of the substituents on the π-electron delocalization and planarity of the bicyclic system. 相似文献
32.
Turrio-Baldassarri L Battistelli CL Iamiceli AL 《Analytical and bioanalytical chemistry》2003,375(4):589-595
Pressurized Fluid Extraction (PFE) was evaluated for the extraction of polycyclic aromatic hydrocarbons (PAHs) and nitro-derivatives from diesel particulate matter. Extraction conditions were set up by performing several tests in which temperature, solvent strength, pressure, and static time were gradually increased. The results obtained on a laboratory test material made of a "lean" (low content of soluble fraction) Diesel particulate matter indicate that very severe conditions were needed in order to obtain better recoveries of the higher molecular weight molecules. Moreover, extraction efficiency seems to be influenced by the amount of soluble matter in the particulate, so that a "lean" particulate appears more difficult to extract. Recoveries of the deuterated standards of certain PAHs (i.e. indeno[1,2,3- cd]pyrene) were incomplete even with the toughest conditions tested. Experiments carried out on a certified material (SRM 1650 from NIST) also indicate that PFE can perform a better extraction of some of the PAHs than the method used for certification, but still incomplete. Comparison of results obtained on the SRM with different extraction techniques suggests that the composition of the extract varies considerably with the extraction technique and conditions. It is relevant to notice that recent Diesel engines produce leaner particulate: for future materials more drastic extraction conditions will be required. 相似文献
33.
Spot overlapping in two-dimensional polyacrylamide gel electrophoresis separations: a statistical study of complex protein maps 总被引:1,自引:0,他引:1
A statistical approach able to extract the information contained in a two-dimenisional polyacrylamide gel electrophoresis (2-D PAGE) separation is here reported. The method is based on the quantitative theory of peak overlapping, a procedure previously developed by the authors and here extended to 2-D separations. The whole map is divided into many strips in order to obtain 1-D separations on which the statistic procedure is applied: the developed algorithms, on the basis of spot experimental data (intensity and spatial coordinates) permit to estimate the intrinsic number of components and to single out the specific order present in spot positions. The procedure was validated on computer-simulated maps. Its applicability to real samples was tested on maps obtained from literature sources. The following important information on protein mixtures can be extracted: (i) the number of proteins can be accurately estimated, on the basis of the spatial coordinates and intensities of spots detected in the 2-D PAGE map; (ii) the model describing distribution of interdistance between adjacent spots can be identified in both the separation dimensions; (iii) the presence of repeated interdistances in spot positions in the maps can be easily singled out: these regularities suggest specific protein modifications. 相似文献
34.
Hydration Behaviour of Mixtures of Cement and Fly Ash with High Sulphate and Chloride Content 总被引:1,自引:0,他引:1
DTA/TG thermoanalytical investigations and X-ray diffractometry were carried out which demonstrate the effect of MSW fly ash
on the hydration reactions of pozzolanic cement. The MSW fly ash has high content of calcium sulphate, alkali chlorides and
heavy metals. During the first curing period the calcium aluminate reacts with the sulphate to form ettringite. In that period
also the presence of syngenite is noted in the pastes. With the growth of the fly ash content of the mixture there is a lengthening
of the period in which the hydration reactions of the calcium silicates are inhibited. Subsequently with the progress of hydration
in the pastes the CSH phase develops and the formation of calcium chloroaluminate phase is observed.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
35.
R. Bucci V. Carunchio A. D. Magrí A. L. Magrì 《Journal of Thermal Analysis and Calorimetry》1985,30(6):1309-1315
Copper(II) complexes of 3- and 4-pyridinealdoxime have been prepared and analyzed by spectroscopic (ir and diffuse reflectance) and thermoanalytical (TG, DTG and DTA) techniques. For both these systems, only species with metal: organic ligand: chloride ratio of 122 were found, and the organic ligand appears as a neutral molecule. The spectral data suggest a polymeric structure where the copper(II) ions are in a distorted octahedral environment.The thermal decompositions occur through the reduction of copper(II) to copper(I) and the conversion of the residual organic ligand into acid amide, as found for dihydrogenbis(pyridine-2-aldoxime) copper(II) chloride, but the initial decomposition temperatures are slightly increased, giving rise to the thermal stability sequence:
Zusammenfassung Kupfer(II)-Komplexe von 3- und 4-Pyridinaldoxim wurden hergestellt und spektroskopisch (IR und diffuse Reflexion) sowie thermoanalytisch (TG, DTG und DTA) analysiert. Für beide Systeme wurden nur Species mit einem Metall:Ligand:Chlorid-Verhältnis von 122 gefunden. Der organische Ligand liegt als neutrales Molekül vor. Die Spektren deuten auf eine polymère Struktur hin, in der die Kupfer(II)-Ionen in einer verzerrten oktaedrischen Koordination vorliegen. Die thermischen Zersetzungen verlaufen über die Reduktion von Cu(II) zu Cu(I) und die Umwandlung des verbleibenden organischen Liganden in Säureamid, wie für Dihydrogen-bis(pyridin-2-aldoxim)-kupfer(II)-chlorid gefunden wurde, aber die Temperaturen des Beginns der Zersetzung und damit die thermische Stabilität steigen in der Reihenfolge [Cu(Py4-CHNOH)2Cl2][Cu(Py3-CHNOH)2Cl2]>[Cu(Py2-CHNOH)2]Cl2 etwas an.
(, ) ( ) 3- 4- . 122, . , . -( -2-)- . , , , : Cu(4-Py-CHNOH)2Cl2Cu(3-Py-CHNOH)2Cl2>Cu(2-Py-CHNOH)2Cl2.相似文献
36.
Wu J Zaleski TJ Valenzano C Khosla C Cane DE 《Journal of the American Chemical Society》2005,127(49):17393-17404
Picromycin/methymycin synthase (PICS) is a modular polyketide synthase (PKS) that is responsible for the biosynthesis of both 10-deoxymethynolide (1) and narbonolide (2), the parent 12- and 14-membered aglycone precursors of the macrolide antibiotics methymycin and picromycin, respectively. PICS module 2 is a dehydratase (DH)-containing module that catalyzes the formation of the unsaturated triketide intermediate using malonyl-CoA as the chain extension substrate. Recombinant PICS module 2+TE, with the PICS thioesterase domain appended to the C-terminus to allow release of polyketide products, was expressed in Escherichia coli. Purified PICS module 2+TE converted malonyl-CoA and 4, the N-acetylcysteamine thioester of (2S,3R)-2-methyl-3-hydroxypentanoic acid, to a 1:2 mixture of the triketide acid (4S,5R)-4-methyl-5-hydroxy-2-heptenoic acid (5) and (3S,4S,5R)-3,5-dihydroxy-4-methyl-n-heptanoic acid-delta-lactone (10) with a combined kcat of 0.6 min(-1). The triketide lactone 10 is formed by thioesterase-catalyzed cyclization of the corresponding d-3-hydroxyacyl-SACP intermediate, a reaction which competes with dehydration catalyzed by the dehydratase domain. PICS module 2+TE showed a strong preference for the syn-diketide-SNAC 4, with a 20-fold greater kcat/K(m) than the anti-(2S,3S)-diketide-SNAC 14, and a 40-fold advantage over the syn-(2R,3S)-diketide-SNAC 13. PICS module 2(DH(0))+TE, with an inactivated DH domain, produced exclusively 10, while three PICS module 2(KR(0))+TE mutants, with inactivated KR domains, produced exclusively or predominantly the unreduced triketide ketolactone, (4S,5R)-3-oxo-4-methyl-5-hydroxy-n-heptanoic acid-delta-lactone (7). These studies establish for the first time the structure and stereochemistry of the intermediates of a polyketide chain elongation cycle catalyzed by a DH-containing module, while confirming the importance of key active site residues in both KR and DH domains. 相似文献
37.
Bingham RJ Findlay JB Hsieh SY Kalverda AP Kjellberg A Perazzolo C Phillips SE Seshadri K Trinh CH Turnbull WB Bodenhausen G Homans SW 《Journal of the American Chemical Society》2004,126(6):1675-1681
In the present study we examine the thermodynamics of binding of two related pyrazine-derived ligands to the major urinary protein, MUP-I, using a combination of isothermal titration calorimetry (ITC), X-ray crystallography, and NMR backbone (15)N and methyl side-chain (2)H relaxation measurements. Global thermodynamics data derived from ITC indicate that binding is driven by favorable enthalpic contributions, rather than the classical entropy-driven hydrophobic effect. Unfavorable entropic contributions from the protein backbone and side-chain residues in the vicinity of the binding pocket are partially offset by favorable entropic contributions at adjacent positions, suggesting a "conformational relay" mechanism whereby increased rigidity of residues on ligand binding are accompanied by increased conformational freedom of side chains in adjacent positions. The principal driving force governing ligand affinity and specificity can be attributed to solvent-driven enthalpic effects from desolvation of the protein binding pocket. 相似文献
38.
39.
Sheng Yang Antonio Gaetano Ricciardulli Dr. Shaohua Liu Dr. Renhao Dong Dr. Martin R. Lohe Alfons Becker Marco A. Squillaci Prof. Paolo Samorì Prof. Klaus Müllen Prof. Xinliang Feng 《Angewandte Chemie (International ed. in English)》2017,56(23):6669-6675
To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1–3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm2 V−1 s−1). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h−1 in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO4 particles deliver a high capacity of 167 mAh g−1 at 1 C rate after 500 cycles. 相似文献
40.
Dr. Maria Laura Tummino Dr. Roberto Nisticò Dr. Chiara Riedo Prof. Debora Fabbri Prof. Marta Cerruti Prof. Giuliana Magnacca 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):660-668
Biowaste-derived substances isolated from green compost (BBS-GC) are environmentally friendly reactants similar to humic substances, which contain multiple functionalities, that are suitable for adsorbing different kinds of pollutants in wastewater. Herein, sodium alginate (derived from brown algae) cross-linked with both Ca2+ ions and BBS-GC in the form of hydrogels and dried films are proposed as green, easy-to-form, and handleable materials for tertiary water treatments. The results show that both hydrogels and films are mechanically stable and can effectively remove differently charged dyes through an adsorption mechanism that can be described by the Freundlich model. BBS-GC-containing gels always performed better than samples prepared without BBS-GC, revealing that such unconventional materials can integrate waste valorization and water decontamination, potentially providing social and environmental benefits. 相似文献