全文获取类型
收费全文 | 1114篇 |
免费 | 92篇 |
国内免费 | 91篇 |
专业分类
化学 | 531篇 |
力学 | 15篇 |
综合类 | 9篇 |
数学 | 636篇 |
物理学 | 106篇 |
出版年
2023年 | 7篇 |
2022年 | 12篇 |
2021年 | 21篇 |
2020年 | 26篇 |
2019年 | 22篇 |
2018年 | 32篇 |
2017年 | 18篇 |
2016年 | 35篇 |
2015年 | 29篇 |
2014年 | 41篇 |
2013年 | 78篇 |
2012年 | 36篇 |
2011年 | 35篇 |
2010年 | 43篇 |
2009年 | 54篇 |
2008年 | 59篇 |
2007年 | 59篇 |
2006年 | 92篇 |
2005年 | 95篇 |
2004年 | 100篇 |
2003年 | 82篇 |
2002年 | 41篇 |
2001年 | 31篇 |
2000年 | 51篇 |
1999年 | 27篇 |
1998年 | 41篇 |
1997年 | 45篇 |
1996年 | 23篇 |
1995年 | 14篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1966年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有1297条查询结果,搜索用时 31 毫秒
1.
本文对Hardy和Littlewood考虑的一个有限三角和做了进一步地研究.通过充分运用Chebyshev多项式和M?bius函数的性质,建立了该有限三角和的一个有趣的恒等式,并得到了一个精确的渐近公式. 相似文献
2.
3.
Nadya Abbood Dr. Tien Duy Vo Dr. Jonas Watzel Dr. Kenan A. J. Bozhueyuek Prof. Dr. Helge B. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(26):e202103963
Bacterial natural products in general, and non-ribosomally synthesized peptides in particular, are structurally diverse and provide us with a broad range of pharmaceutically relevant bioactivities. Yet, traditional natural product research suffers from rediscovering the same scaffolds and has been stigmatized as inefficient, time-, labour- and cost-intensive. Combinatorial chemistry, on the other hand, can produce new molecules in greater numbers, cheaper and in less time than traditional natural product discovery, but also fails to meet current medical needs due to the limited biologically relevant chemical space that can be addressed. Consequently, methods for the high throughput generation of new natural products would offer a new approach to identifying novel bioactive chemical entities for the hit to lead phase of drug discovery programs. As a follow-up to our previously published proof-of-principle study on generating bipartite type S non-ribosomal peptide synthetases (NRPSs), we now envisaged the de novo generation of non-ribosomal peptides (NRPs) on an unreached scale. Using synthetic zippers, we split NRPSs in up to three subunits and rapidly generated different bi- and tripartite NRPS libraries to produce 49 peptides, peptide derivatives, and de novo peptides at good titres up to 145 mg L−1. A further advantage of type S NRPSs not only is the possibility to easily expand the created libraries by re-using previously created type S NRPS, but that functions of individual domains as well as domain-domain interactions can be studied and assigned rapidly. 相似文献
4.
《Annals of Pure and Applied Logic》2022,173(8):103135
We further develop a forcing notion known as Coding with Perfect Trees and show that this poset preserves, in a strong sense, definable P-points, definable tight MAD families and definable selective independent families. As a result, we obtain a model in which , each of , , has a witness and there is a well-order of the reals. Note that both the complexity of the witnesses of the above combinatorial cardinal characteristics, as well as the complexity of the well-order are optimal. In addition, we show that the existence of a well-order of the reals is consistent with and each of the following: , , , where the smaller cardinal characteristics have co-analytic witnesses.Our methods allow the preservation of only sufficiently definable witnesses, which significantly differs from other preservation results of this type. 相似文献
5.
《Journal of separation science》2017,40(14):2895-2905
Bioactive equivalent combinatorial components play a critical role in herbal medicines. However, how to discover and enrich them efficiently is a question for herbal pharmaceuticals researchers. In our work, a novel two‐dimensional reversed‐phase/hydrophilic interaction high‐performance liquid chromatography method was established to perform real‐time components trapping and combining for preparation and isolation of coeluting components. Arenaria kansuensis was taken as an example, and solid‐phase extraction coupled with liquid–liquid extraction as a simple and efficient method for enriching trace components, reversed phase column coupled with hydrophilic interaction liquid chromatography XAmide column as two‐dimensional chromatography technology for isolation and preparation of coeluting constituents, enzyme‐linked immune‐sorbent assay as bio‐guided assay, and anti‐inflammatory bioactivity evaluation for bioactive constituents. A combination of 12 β‐carboline alkaloids was identified as anti‐inflammatory bioactive equivalent combinatorial components from A. kansuensis , which accounts for 1.9% w/w of original A. kansuensis . This work answers the key question of which are real anti‐inflammatory components from A. kansuensis and provides a fast and efficient approach for discovering and enriching trace β‐carboline alkaloids from herbal medicines for the first time. More importantly, the discovery of bioactive equivalent combinatorial components could improve the quality control of herbal products and inspire a herbal medicine based on combinatorial therapeutics. 相似文献
6.
Models based on sparse graphs are of interest to many communities: they appear as basic models in combinatorics, probability theory, optimization, statistical physics, information theory, and more applied fields of social sciences and economics. Different notions of similarity (and hence convergence) of sparse graphs are of interest in different communities. In probability theory and combinatorics, the notion of Benjamini‐Schramm convergence, also known as left‐convergence, is used quite frequently. Statistical physicists are interested in the the existence of the thermodynamic limit of free energies, which leads naturally to the notion of right‐convergence. Combinatorial optimization problems naturally lead to so‐called partition convergence, which relates to the convergence of optimal values of a variety of constraint satisfaction problems. The relationship between these different notions of similarity and convergence is, however, poorly understood. In this paper we introduce a new notion of convergence of sparse graphs, which we call Large Deviations or LD‐convergence, and which is based on the theory of large deviations. The notion is introduced by “decorating” the nodes of the graph with random uniform i.i.d. weights and constructing corresponding random measures on and . A graph sequence is defined to be converging if the corresponding sequence of random measures satisfies the Large Deviations Principle with respect to the topology of weak convergence on bounded measures on . The corresponding large deviations rate function can be interpreted as the limit object of the sparse graph sequence. In particular, we can express the limiting free energies in terms of this limit object. We then establish that LD‐convergence implies the other three notions of convergence discussed above, and at the same time establish several previously unknown relationships between the other notions of convergence. In particular, we show that partition‐convergence does not imply left‐ or right‐convergence, and that right‐convergence does not imply partition‐convergence. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 51, 52–89, 2017 相似文献
7.
Iuliana-Marilena Andrei Dmytro Strilets Dr. Shixin Fa Marc Baaden Prof. Tomoki Ogoshi Dr. Mihail Barboiu 《Angewandte Chemie (International ed. in English)》2023,62(42):e202310812
Artificial water channels (AWCs) that selectively transport water and reject ions through bilayer membranes have potential to act as synthetic Aquaporins (AQPs). AWCs can have a similar osmotic permeability, better stability, with simpler manufacture on a larger-scale and have higher functional density and surface permeability when inserted into the membrane. Here, we report the screening of combinatorial libraries of symmetrical and unsymmetrical rim-functionalized PAs A – D that are able to transport ca. 107–108 water molecules/s/channel, which is within 1 order of magnitude of AQPs’ and show total ion and proton rejection. Among the four channels, C and D are 3–4 times more water permeable than A and B when inserted in bilayer membranes. The binary combinations of A – D with different molar ratios could be expressed as an independent (linear ABA ), a recessive (inhibition AB , AC , DB , ACA ), or a dominant (amplification, DBD ) behavior of the water net permeation events. 相似文献
8.
Dr. Masahito Yoshida Yoshitaka Ishida Kenta Adachi Hayato Murase Dr. Hiroshi Nakagawa Prof.Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18417-18430
The solid‐phase combinatorial synthesis of cyclodepsipeptide destruxin E has been demonstrated. The combinatorial synthesis of cyclization precursors 8 was achieved by using a split and pool method on SynPhase Lanterns. The products were successfully macrolactonized in parallel in the solution phase by using 2‐methyl‐6‐nitrobenzoic anhydride and 4‐(dimethylamino)pyridine N‐oxide to afford macrolactones 9 , and the subsequent formation of an epoxide in the side chain gave 18 member destruxin E analogues 6 . Biological evaluation of analogues 6 indicated that the N‐MeAla residue was crucial to the induction of morphological changes in osteoclast‐like multinuclear cells (OCLs). Based on structure–activity relationships, azido‐containing analogues 15 were then designed for use as a molecular probe. The synthesis and biological evaluation of analogues 15 revealed that 15 b , in which the Ile residue was replaced with a Lys(N3) residue, induced morphological changes in OCLs at a sufficient concentration, and modification around the Ile residue would be tolerated for attachment of a chemical tag toward the target identification of destruxin E ( 1 ). 相似文献
9.
Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes 下载免费PDF全文
Qing Ji Ha T. M. Le Dr. Xiqu Wang Dr. Yu‐Sheng Chen Dr. Tatyana Makarenko Prof. Allan J. Jacobson Prof. Ognjen Š. Miljanić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17205-17209
Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m2 g?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation. 相似文献
10.
Identification of Structure–Activity Relationships from Screening a Structurally Compact DNA‐Encoded Chemical Library 下载免费PDF全文
Dr. Raphael M. Franzini Dr. Torun Ekblad Dr. Nan Zhong Moreno Wichert Willy Decurtins Angela Nauer Mauro Zimmermann Dr. Florent Samain Dr. Jörg Scheuermann Dr. Peter J. Brown Prof. Dr. Jonathan Hall Dr. Susanne Gräslund Prof. Dr. Herwig Schüler Prof. Dr. Dario Neri 《Angewandte Chemie (International ed. in English)》2015,54(13):3927-3931
Methods for the rapid and inexpensive discovery of hit compounds are essential for pharmaceutical research and DNA‐encoded chemical libraries represent promising tools for this purpose. We here report on the design and synthesis of DAL‐100K, a DNA‐encoded chemical library containing 103 200 structurally compact compounds. Affinity screening experiments and DNA‐sequencing analysis provided ligands with nanomolar affinities to several proteins, including prostate‐specific membrane antigen and tankyrase 1. Correlations of sequence counts with binding affinities and potencies of enzyme inhibition were observed and enabled the identification of structural features critical for activity. These results indicate that libraries of this type represent a useful source of small‐molecule binders for target proteins of pharmaceutical interest and information on structural features important for binding. 相似文献