全文获取类型
收费全文 | 5720篇 |
免费 | 320篇 |
国内免费 | 25篇 |
专业分类
化学 | 4319篇 |
晶体学 | 12篇 |
力学 | 130篇 |
数学 | 818篇 |
物理学 | 786篇 |
出版年
2023年 | 60篇 |
2022年 | 33篇 |
2021年 | 110篇 |
2020年 | 119篇 |
2019年 | 128篇 |
2018年 | 77篇 |
2017年 | 74篇 |
2016年 | 261篇 |
2015年 | 206篇 |
2014年 | 202篇 |
2013年 | 312篇 |
2012年 | 399篇 |
2011年 | 425篇 |
2010年 | 275篇 |
2009年 | 243篇 |
2008年 | 339篇 |
2007年 | 299篇 |
2006年 | 315篇 |
2005年 | 299篇 |
2004年 | 262篇 |
2003年 | 192篇 |
2002年 | 208篇 |
2001年 | 113篇 |
2000年 | 90篇 |
1999年 | 81篇 |
1998年 | 71篇 |
1997年 | 95篇 |
1996年 | 75篇 |
1995年 | 76篇 |
1994年 | 48篇 |
1993年 | 51篇 |
1992年 | 34篇 |
1991年 | 25篇 |
1990年 | 23篇 |
1989年 | 23篇 |
1988年 | 20篇 |
1987年 | 17篇 |
1986年 | 15篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 15篇 |
1981年 | 18篇 |
1978年 | 19篇 |
1974年 | 14篇 |
1973年 | 21篇 |
1962年 | 29篇 |
1961年 | 15篇 |
1956年 | 12篇 |
1955年 | 12篇 |
排序方式: 共有6065条查询结果,搜索用时 31 毫秒
71.
72.
E. Abel 《Monatshefte für Chemie / Chemical Monthly》1954,85(1):227-234
Zusammenfassung Don Geschwindigkeitsbeziehungen, die unter zeitlicher Verfolgung der Autoxydation von Ferroion erhalten worden sind, werden Rektionsmechanismen zugeordnet: der charakteristische Aciditätseinfluß sei durch einen Primärschritt bedingt, der in electron transfer zwischen O2 und OH-Ion besteht, unter gleichzeitiger Anlagerung von OH; eine entsprechende Struktur wird auch jenem Mechanismus zuzuordnen versucht, der zu quadratischer Abhängigkeit der Autoxydationsgeschwindigkeit von der Ferroionkonzentration führt. 相似文献
73.
Thoma G Streiff MB Katopodis AG Duthaler RO Voelcker NH Ehrhardt C Masson C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):99-117
Polyvalent carbohydrate-protein interactions occur frequently in biology, particularly in recognition events on cellular membranes. Collectively, they can be much stronger than corresponding monovalent interactions, rendering it difficult to control them with individual small molecules. Artificial macromolecules have been used as polyvalent ligands to inhibit polyvalent processes; however, both reproducible synthesis and appropriate characterization of such complex entities is demanding. Herein, we present an alternative concept avoiding conventional macromolecules. Small glycodendrimers which fulfill single molecule entity criteria self-assemble to form non-covalent nanoparticles. These particles-not the individual molecules-function as polyvalent ligands, efficiently inhibiting polyvalent processes both in vitro and in vivo. The synthesis and characterization of these glycodendrimers is described in detail. Furthermore, we report on the characterization of the non-covalent nanoparticles formed and on their biological evaluation. 相似文献
74.
E. Anklam Maria Rosa Bassani Thomas Eiberger Stefan Kriebel Markus Lipp Reinhard Matissek 《Analytical and bioanalytical chemistry》1997,357(7):981-984
Pyrolysis Mass Spectrometry (Py-MS) was used for the discrimination of cocoa butters from other vegetable fats. Mass spectra
ranging from 50 amu to 250 amu were analyzed by principal component analysis (PCA) and with neural nets. The application of
neural nets leads to a good discrimination between the two classes. Detailed analysis of the nets revealed that only the first
60 masses were used within the net. The use of PCA requires a careful selection of the number of masses included in the calculation.
Canonical variance analysis was applied to determine the significant masses. Optimal performance of PCA was observed only
using the first 22 significant masses. Most of these masses were different from the ones used by the neural net. It seems
that the mass spectra obtained by Py-MS contain sufficient information for the discrimination of pure cocoa butter from other
vegetable fats, but none of the methods seems to be able to extract all information available. Neural net provides a very
robust method for this task and no prior data selection was necessary.
Received: 13 May 1996 / Revised: 7 August 1996 / Accepted: 7 August 1996 相似文献
75.
Martin Sukopp Luciana Marinelli Markus Heller Trixi Brandl SimonL. Goodman ReinhardW. Hoffmann Horst Kessler 《Helvetica chimica acta》2002,85(12):4442-4452
The (3R,5S,6E,8S,10R)‐11‐amino‐3,5,8,10‐tetramethylundec‐6‐enoic acid (ATUA; 1 ), which was designed as a βII′‐turn mimic according to the concepts of allylic strain and 2,4‐dimethylpentane units, was incorporated into a cyclic RGD peptide. The three‐dimensional structure of cyclo(‐RGD‐ATUA‐) (=cyclo(‐Arg‐Gly‐Asp‐ATUA‐)) 4 in H2O was determined by NMR techniques, distance geometry calculations and molecular‐dynamics simulations. The RGD sequence of 4 shows high conformational flexibility but some preference for an extended conformation. The structural features of the RGD sequence of 4 were compared with the RGD moiety of cyclo(‐RGDfV‐) (=cyclo(‐Arg‐Gly‐Asp‐D ‐Phe‐Val‐)). In contrast to cyclo(‐RGDfV‐), which is a highly active αvβ3 antagonist and selective against αIIbβ3, cyclo(‐RGD‐ATUA‐) shows a lower activity and selectivity. The structure of the ATUA residue in the cyclic peptide resembles a βII′‐turn‐like conformation. Its middle part, adjacent to the C?C bond, strongly prefers the designed and desired structure. 相似文献
76.
The addition of carboxylic acids to dimethylamino-propinal ( 1a ) and 4-dimethyl-amino-but-3-in-2-on ( 1b ) gives, after rearrangement of the very instable primary adducts ( 2 ), Z-3-acetoxy-N,N-dimethylacrylamides and -crotonamides 3 to 8 in excellent yields and in a stereospecific manner. Similarly, the adducts of HCl and HBr to the alkynes 1a and 1b may be rearranged at low temperature by traces of acid to cis/trans equilibria of 3-halo-acrylamides and -crotonamides 9 and 10 . - On the other hand, treatment of 3-alkoxy-3-dimethylaminoacrolein with traces of acid yields alkylesters of E-3-dimethylaminoacrylic acid ( 12 , X = OR). - The preparative aspects of the rearrangement are discussed, and a brief outline of the spectroscopic properties of the compounds 3 to 8 is given. 相似文献
77.
78.
Loferer MJ Webb BM Grant GH Liedl KR 《Journal of the American Chemical Society》2003,125(4):1072-1078
QM/MM methods were used to study the isomerization step from (2R)-methylmalonyl-CoA to succinyl-CoA. A pathway via a "fragmentation-recombination" mechanism is ruled out on energetic grounds. For the other radicalic pathway, involving an addition recombination step, geometries and vibrational contributions have been determined, and a barrier height of 11.70 kcal/mol was found. The effect of adjacent hydrogen-donating groups was found to reduce the energy barrier by 1-2 kcal/mol each and thus to provide a significant catalytic effect for this reaction. By means of molecular dynamics studies, the stereochemistry of the methylmalonyl-CoA mutase catalyzed reaction was examined. It is shown that TYR89 is essential for maintaining stereoselectivity of the abstraction of a hydrogen in the backreaction. The subsequent selective formation of one isomer of methylmalonyl-CoA is probably due to the presence of a bulky side chain. 相似文献
79.
The energetics and dynamics of double proton transfer (DPT) is investigated theoretically for the Watson-Crick conformation of the guanine-cytosine (GC) base pair. Using semiempirical density functional theory the isolated and DNA-embedded GC pair is considered. Differences in the energetics and dynamics of DPT thus addresses the question of how relevant studies of isolated base pairs are for the understanding of processes occurring in DNA. Two-dimensional potential energy surfaces involving the transferring hydrogen atoms and the proton donors and acceptors are presented for both systems. The DPT reaction is accompanied by a contraction of the distance between the two bases with virtually identical energetic barriers being 18.8 and 18.7 kcal/mol for the isolated and DNA-embedded system, respectively. However, the transition state for DPT in the DNA-embedded GC pair is offset by 0.1 A to larger N-H separation compared to the isolated GC pair. Using activated ab initio molecular dynamics, DPT is readily observed for the isolated base pair with a minimal amount of 21.4 kcal/mol of initial average kinetic energy along the DPT normal mode vector. On a time scale of approximately 100 fs DPT has occurred and the excess energy is redistributed. For the DNA-embedded GC pair considerably more kinetic energy is required (30.0 kcal/mol) for DPT and the process is completed within one hydrogen vibration. The relevance of studies of isolated base pairs and base pair analogs in regard of reactions or properties involving DNA is discussed. 相似文献
80.
Scherer LJ Merz L Constable EC Housecroft CE Neuburger M Hermann BA 《Journal of the American Chemical Society》2005,127(11):4033-4041
We describe the synthesis and a novel approach to the conformational analysis of 2,2'-bipyridines (bpy) bearing aromatic rich Frechet-type dendritic wedges of the first and second generation as substituents. The evaporation of solutions of these new ligands on graphite surfaces under ambient conditions results in the formation of self-organized monolayers. Scanning tunneling microscopy (STM) investigations of the monolayers under ambient conditions (air, 298 K) gave images at submolecular and near-atomic resolution. The analysis of the STM images includes the following processes: (i) identification and reproduction of potential homoconformational domains, (ii) exclusion of improper data using quality criteria for drift and feedback artifacts, (iii) compilation of running averages and checking for averaging artifacts, (iv) analysis of three-dimensional and contour plots, (v) calculation of the HOMO properties of the free molecules, and (vi) final conformational assignment based on all accessible information. Following this procedure, two different conformations could be assigned to domains observed in the monolayers of the first-generation (G1) and second-generation (G2) dendritic compounds. Homoconformational domains are observed side-by-side. The different conformations arise from syn or anti arrangements at the ether substituents. An additional conformational effect is found upon treating the G1 domains with HCl gas, when a partial rearrangement of the bpy from trans to cis occurs, concomitant with protonation. 相似文献