全文获取类型
收费全文 | 81篇 |
免费 | 7篇 |
专业分类
化学 | 55篇 |
力学 | 2篇 |
数学 | 8篇 |
物理学 | 23篇 |
出版年
2023年 | 5篇 |
2021年 | 1篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2016年 | 6篇 |
2015年 | 1篇 |
2014年 | 4篇 |
2013年 | 9篇 |
2012年 | 3篇 |
2011年 | 6篇 |
2010年 | 1篇 |
2009年 | 2篇 |
2008年 | 7篇 |
2007年 | 10篇 |
2006年 | 4篇 |
2005年 | 4篇 |
2004年 | 2篇 |
2002年 | 1篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 1篇 |
排序方式: 共有88条查询结果,搜索用时 15 毫秒
1.
2.
Jun.-Prof. Dr. Max M. Hansmann Patrick W. Antoni Henner Pesch 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5831-5836
We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′-diaryl-1,2,3-triazolium and N,N′-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong σ-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs. 相似文献
3.
We introduce a novel simulation method, model hopping, that enhances sampling of low-energy configurations in complex systems. The approach is illustrated for a protein-folding problem. Thermodynamic quantities of proteins with up to 46 residues are evaluated from all-atom simulations with this method. 相似文献
4.
Hansmann UH 《The Journal of chemical physics》2004,120(1):417-422
A generalized-ensemble technique, multicanonical sampling, is used to study the folding of a 34-residue human parathyroid hormone fragment. An all-atom model of the peptide is employed and the protein-solvent interactions are approximated by an implicit solvent. Our results demonstrate that generalized-ensemble simulations are well suited to sample low-energy structures of such large polypeptides. Configurations with a root-mean-square deviation to the crystal structure of less than 1 A are found. Finally, we discuss limitations of our implicit solvent model. 相似文献
5.
We report on multicanonical simulations of the helix-coil transition of a polypeptide. The nature of this transition was studied by calculating partition function zeros and the finite size scaling of various quantities. New estimates for critical exponents are presented. 相似文献
6.
We prove Lieb-Thirring-type bounds on eigenvalues of non-selfadjoint Jacobi operators, which are nearly as strong as those
proven previously for the case of selfadjoint operators by Hundertmark and Simon. We use a method based on determinants of
operators and on complex function theory, extending and sharpening earlier work of Borichev, Golinskii and Kupin. 相似文献
7.
Hatch A Hansmann G Murthy SK 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):4257-4264
Microfluidic adhesion-based cell separation systems are of interest in clinical and biological applications where small sample volumes must be processed efficiently and rapidly. While the ability to capture rare cells from complex suspensions such as blood using microfluidic systems has been demonstrated, few methods exist for rapid and nondestructive release of the bound cells. Such detachment is critical for applications in tissue engineering and cell-based therapeutics in contrast with diagnostics wherein immunohistochemical, proteomic, and genomic analyses can be carried out by simply lysing captured cells. This paper demonstrates how the incorporation of four-arm amine-terminated poly(ethylene glycol) (PEG) molecules along with antibodies within alginate hydrogels can enhance the ability of the hydrogels to capture endothelial progenitor cells (EPCs) from whole human blood. The hydrogel coatings are applied conformally onto pillar structures within microfluidic channels and their dissolution with a chelator allows for effective recovery of EPCs following capture. 相似文献
8.
Summary The probability to predict correctly a protein structure can be enhanced through introduction of spatial constraints – either
from NMR experiments or from homologous structures. However, the additional constraints lead often to new local energy minima
and worse sampling efficiency in simulations. In this work, we present a new parallel tempering variant that alleviates the
energy barriers resulting from spatial constraints and therefore yields to an enhanced sampling in structure prediction simulations. 相似文献
9.
Tobias Ullrich Piermaria Pinter Julian Messelberger Philipp Haines Ramandeep Kaur Jun.-Prof. Dr. Max M. Hansmann Dr. Dominik Munz Prof. Dr. Dirk M. Guldi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7980-7988
Herein, we present a new class of singlet fission (SF) materials based on diradicaloids of carbene scaffolds, namely cyclic (alkyl)(amino)carbenes (CAACs). Our modular approach allows the tuning of two key SF criteria: the steric factor and the diradical character. In turn, we modified the energy landscapes of excited states in a systematic manner to accommodate the needs for SF. We report the first example of intermolecular SF in solution by dimer self-assembly at cryogenic temperatures. 相似文献
10.
Dr. Andreas Eitzinger Justus Reitz Patrick W. Antoni Prof. Dr. Herbert Mayr Dr. Armin R. Ofial Jun.-Prof. Max M. Hansmann 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309790
A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2Et)2, which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2(20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2(20 °C)=sN(N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles. 相似文献