全文获取类型
收费全文 | 1575篇 |
免费 | 91篇 |
国内免费 | 11篇 |
专业分类
化学 | 937篇 |
晶体学 | 5篇 |
力学 | 45篇 |
数学 | 411篇 |
物理学 | 279篇 |
出版年
2024年 | 4篇 |
2023年 | 25篇 |
2022年 | 26篇 |
2021年 | 35篇 |
2020年 | 45篇 |
2019年 | 46篇 |
2018年 | 32篇 |
2017年 | 24篇 |
2016年 | 76篇 |
2015年 | 72篇 |
2014年 | 69篇 |
2013年 | 113篇 |
2012年 | 116篇 |
2011年 | 155篇 |
2010年 | 88篇 |
2009年 | 52篇 |
2008年 | 95篇 |
2007年 | 86篇 |
2006年 | 82篇 |
2005年 | 69篇 |
2004年 | 67篇 |
2003年 | 54篇 |
2002年 | 44篇 |
2001年 | 18篇 |
2000年 | 17篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 23篇 |
1994年 | 11篇 |
1993年 | 3篇 |
1992年 | 12篇 |
1991年 | 5篇 |
1990年 | 11篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1979年 | 4篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1921年 | 1篇 |
1918年 | 1篇 |
1916年 | 2篇 |
排序方式: 共有1677条查询结果,搜索用时 15 毫秒
991.
Dr. Jing Sun Julian Vogel Lisa Chen A. Lennart Schleper Tim Bergner Prof. Dr. Alexander J. C. Kuehne Prof. Dr. Max von Delius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(13):e202104116
The aqueous self-assembly of amphiphiles into aggregates such as micelles and vesicles has been widely investigated over the past decades with applications ranging from materials science to drug delivery. The combination of characteristic properties of nucleic acids and amphiphiles is of substantial interest to mimic biological self-organization and compartmentalization. Herein, we present ribose- and ribonucleotide-based amphiphiles and investigate their self-assembly as well as their fundamental reactivity. We found that various types of aggregates are formed, ranging in size from nanometers to micrometers and all amphiphiles exhibit aggregation-induced emission (AIE) in solution as well as in the solid state. We also observed that the addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) leads to rapid and selective dimerization of the amphiphiles into pyrophosphates, which decreases the critical aggregation concentration (CAC) by a factor of 25 when compared to the monomers. Since the propensity for amphiphile dimerization is correlated with their tendency to self-assemble, our results may be relevant for the formation of rudimentary compartments under prebiotic conditions. 相似文献
992.
Arne Brahms Dr. Andrey N. Pravdivtsev Tim Stamp Frowin Ellermann Prof. Dr. Frank D. Sönnichsen Prof. Dr. Jan-Bernd Hövener Prof. Dr. Rainer Herges 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(55):e202201210
The hyperpolarization of nuclear spins has enabled unique applications in chemistry, biophysics, and particularly metabolic imaging. Parahydrogen-induced polarization (PHIP) offers a fast and cost-efficient way of hyperpolarization. Nevertheless, PHIP lags behind dynamic nuclear polarization (DNP), which is already being evaluated in clinical studies. This shortcoming is mainly due to problems in the synthesis of the corresponding PHIP precursor molecules. The most widely used DNP tracer in clinical studies, particularly for the detection of prostate cancer, is 1-13C-pyruvate. The ideal derivative for PHIP is the deuterated vinyl ester because the spin physics allows for 100 % polarization. Unfortunately, there is no efficient synthesis for vinyl esters of β-ketocarboxylic acids in general and pyruvate in particular. Here, we present an efficient new method for the preparation of vinyl esters, including 13C labeled, fully deuterated vinyl pyruvate using a palladium-catalyzed procedure. Using 50 % enriched parahydrogen and mild reaction conditions, a 13C polarization of 12 % was readily achieved; 36 % are expected with 100 % pH2. Higher polarization values can be potentially achieved with optimized reaction conditions. 相似文献
993.
Dr. Tim Schleif 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(56):e202201775
Quantum mechanical tunneling has long been recognized as an important phenomenon when considering transformations dominated by a lightweight hydrogen atom. Tunneling of heavier atoms like carbon, initially dismissed as negligible, has seen a quickly increasing number of computationally predicted and/or experimentally confirmed examples over the last decade, thus highlighting its importance for a wide variety of reactions. However, no common structural motif has been pointed out within these seemingly unconnected examples, strongly limiting the predictability of the impact of heavy-atom tunneling on a given reaction. This Concept article will provide this perspective and showcase how the recognition of the formation and cleavage of three-membered rings as common motif can inform the prediction of and research into heavy-atom tunneling reactions. 相似文献
994.
We propose a framework for eliciting and aggregating pairwise preference relations based on the assumption of an underlying fuzzy partial order. We also propose some linear programming optimization methods for ensuring consistency either as part of the aggregation phase or as a pre- or post-processing task. We contend that this framework of pairwise-preference relations, based on the Kemeny distance, can be less sensitive to extreme or biased opinions and is also less complex to elicit from experts. We provide some examples and outline their relevant properties and associated concepts. 相似文献
995.
Dr. Nikolaos G. Moustakas Felix Lorenz Dr. Martin Dilla Dr. Tim Peppel Prof. Dr. Jennifer Strunk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17213-17219
Evidence is provided that in a gas-solid photocatalytic reaction the removal of photogenerated holes from a titania (TiO2) photocatalyst is always detrimental for photocatalytic CO2 reduction. The coupling of the reaction to a sacrificial oxidation reaction hinders or entirely prohibits the formation of CH4 as a reduction product. This agrees with earlier work in which the detrimental effect of oxygen-evolving cocatalysts was demonstrated. Photocatalytic alcohol oxidation or even overall water splitting proceeds in these reaction systems, but carbon-containing products from CO2 reduction are no longer observed. H2 addition is also detrimental, either because it scavenges holes or because it is not an efficient proton donor on TiO2. The results are discussed in light of previously suggested reaction mechanisms for photocatalytic CO2 reduction. The formation of CH4 from CO2 is likely not a linear sequence of reduction steps but includes oxidative elementary steps. Furthermore, new hypotheses on the origin of the required protons are suggested. 相似文献
996.
Tim Hawly Fabian Streller Manuel Johnson Dr. Sandra Miguez-Lago Dr. Natalie Hammer Dr. Frank Hampel Dustin Vivod Prof. Dr. Dirk Zahn Prof. Dr. Milan Kivala Robert Branscheid Prof. Dr. Erdmann Spiecker Prof. Dr. Rainer H. Fink 《Chemphyschem》2021,22(11):1079-1087
The ability of a series of bridged triarylamines, so-called N-heterotriangulenes, to form multilayer-type 2D-extended films via a solution-based processing method was examined using complementary microscopic techniques. We found that the long-range order, crystallinity, and layer thickness decisively depend on the nature of the substituents attached to the polycyclic backbone. Owing to their flat core unit, compounds exhibiting a carbonyl unit at the bridge position provide a superior building block as compared to thioketone-bridged derivatives. In addition, nature and length of the peripheral substituents affect the orientation of the aromatic core unit within highly crystalline films. Hence, our results stress the significance of a suitable molecular framework and provide deeper understanding of structure formation in 2D-confined surroundings for such compounds. 相似文献
997.
The prominence of endogenous peptide ligands targeted to receptors makes peptides with the desired binding activity good molecular scaffolds for drug development. Minor modifications to a peptide's primary sequence can significantly alter its binding properties with a receptor, and screening collections of peptide mutants is a useful technique for probing the receptor–ligand binding domain. Unfortunately, the combinatorial growth of such collections can limit the number of mutations which can be explored using structure‐based molecular docking techniques. Genetic algorithm managed peptide mutant screening (GAMPMS) uses a genetic algorithm to conduct a heuristic search of the peptide's mutation space for peptides with optimal binding activity, significantly reducing the computational requirements of the virtual screening. The GAMPMS procedure was implemented and used to explore the binding domain of the nicotinic acetylcholine receptor (nAChR) ‐isoform with a library of 64,000 α‐conotoxin (α‐CTx) MII peptide mutants. To assess GAMPMS's performance, it was compared with a virtual screening procedure that used AutoDock to predict the binding affinity of each of the α‐CTx MII peptide mutants with the ‐nAChR. The GAMPMS implementation performed AutoDock simulations for as few as 1140 of the 64,000 α‐CTx MII peptide mutants and could consistently identify a set of 10 peptides with an aggregated binding energy that was at least 98% of the aggregated binding energy of the 10 top peptides from the exhaustive AutoDock screening. © 2015 Wiley Periodicals, Inc. 相似文献
998.
999.
In a result generalising the Ehresmann–Schein–Nambooripad Theorem relating inverse semigroups to inductive groupoids, Lawson has shown that Ehresmann semigroups correspond to certain types of ordered (small) categories he calls Ehresmann categories. An important special case of this is the correspondence between two-sided restriction semigroups and what Lawson calls inductive categories. Gould and Hollings obtained a one-sided version of this last result, by establishing a similar correspondence between left restriction semigroups and certain ordered partial algebras they call inductive constellations (a general constellation is a one-sided generalisation of a category). We put this one-sided correspondence into a rather broader setting, at its most general involving left congruence D-semigroups (which need not satisfy any semiadequacy condition) and what we call co-restriction constellations, a finitely axiomatized class of partial algebras. There are ordered and unordered versions of our results. Two special cases have particular interest. One is that the class of left Ehresmann semigroups (the natural one-sided versions of Lawson’s Ehresmann semigroups) corresponds to the class of co-restriction constellations satisfying a suitable semiadequacy condition. The other is that the class of ordered left Ehresmann semigroups (which generalise left restriction semigroups and for which semigroups of binary relations equipped with domain operation and the inclusion order are important examples) corresponds to a class of ordered constellations defined by a straightforward weakening of the inductive constellation axioms. 相似文献
1000.