全文获取类型
收费全文 | 684篇 |
免费 | 18篇 |
国内免费 | 1篇 |
专业分类
化学 | 496篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 79篇 |
物理学 | 122篇 |
出版年
2023年 | 8篇 |
2022年 | 10篇 |
2021年 | 9篇 |
2020年 | 6篇 |
2019年 | 9篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 10篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 37篇 |
2012年 | 29篇 |
2011年 | 46篇 |
2010年 | 24篇 |
2009年 | 18篇 |
2008年 | 35篇 |
2007年 | 35篇 |
2006年 | 40篇 |
2005年 | 32篇 |
2004年 | 29篇 |
2003年 | 38篇 |
2002年 | 26篇 |
2001年 | 3篇 |
2000年 | 7篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 10篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 17篇 |
1981年 | 13篇 |
1980年 | 3篇 |
1979年 | 11篇 |
1978年 | 13篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1973年 | 2篇 |
排序方式: 共有703条查询结果,搜索用时 15 毫秒
81.
Martin B. Duriska Dr. Suzanne M. Neville Dr. Boujemaa Moubaraki Dr. John D. Cashion Assoc. Prof Gregory J. Halder Dr. Karena W. Chapman Dr. Chérif Balde Jean‐François Létard Dr. Keith S. Murray Prof. Cameron J. Kepert Prof. Stuart R. Batten Assoc. Prof. 《Angewandte Chemie (International ed. in English)》2009,48(14):2428-2428
Continuous switching between high‐spin and low‐spin magnetic states can be accomplished by irradiation with red and green laser light, respectively. In their Communication on page 2549 ff., S. R. Batten and co‐workers report a metallo‐supramolecule that undergoes spin crossover (SCO) switching induced by temperature change or light irradiation. The SCO behavior is also dependent on the presence and nature of intercalated solvent molecules within the porous crystal structure.
82.
Lucie Appy Anaïs Depaix Xavier Bantreil Frédéric Lamaty Suzanne Peyrottes 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):930-931
AbstractWe have developed original one-pot and protecting group-free approaches, which are also user-friendly and reliable, to synthesize nucleotides and derivatives starting from nucleoside 5’-monophosphates. Both methods present convenient set-up, i.e., non-dry solvents and reagents, substrates in their sodium or acid form, and commercially available and cheap phosphorus reagents as sodium and potassium salts. 相似文献
83.
Amanda M Goh Kylie J Walters Suzanne Elsasser Rati Verma Raymond J Deshaies Daniel Finley Peter M Howley 《BMC biochemistry》2008,9(1):4
Background
The delivery of ubiquitinated proteins to the proteasome for degradation is a key step in the regulation of the ubiquitin-proteasome pathway, yet the mechanisms underlying this step are not understood in detail. The Rad23 family of proteins is known to bind ubiquitinated proteins through its two ubiquitin-associated (UBA) domains, and may participate in the delivery of ubiquitinated proteins to the proteasome through docking via the Rad23 ubiquitin-like (UBL) domain. 相似文献84.
Normal and lateral forces between two opposing monolayers of grafted polymer nanoparticles (NPs) were measured using the Surface Forces Apparatus in a humid atmosphere. The NPs made of N, N-diethylacrylamide and 2-hydroxyethyl methacrylate have a hydrodynamic diameter of ca. 660 nm at 25 degrees C. The effect of surface roughness was studied by creating surface asperities using different NP grafting densities ranging from 0.41 to 2.63 NPs/mum (2). An increase in the NPs grafting density gave rise to an increase in surface roughness and to a deformation of the nanoparticles caused by the lateral pressure between neighboring particles. An elastoplastic behavior of the nanoparticles was observed for large grafting densities, while a purely elastic behavior was observed for small grafting densities. The lateral forces measured between two opposing NP monolayers sliding past each other followed Amontons' law for all grafting densities. The friction coefficient between the surfaces appeared to increase significantly with an increase in surface roughness, which was inherent to an increase in the elastoplastic behavior of the NP monolayers. 相似文献
85.
Scarpellini M Gätjens J Martin OJ Kampf JW Sherman SE Pecoraro VL 《Inorganic chemistry》2008,47(9):3584-3593
In view of the biological and commercial interest in models for Oxalate Decarboxylases (OxDC) and Oxalate Oxidases (OxOx), we have synthesized and characterized three new Mn (II) complexes ( 1- 3) employing N3O-donor amino-carboxylate ligands (TCMA, 1,4,7-triazacyclononane- N-acetic acid; K (i) Pr 2TCMA, potassium 1,4-diisopropyl-1,4,7-triazacyclononane- N-acetate; and KBPZG, potassium N,N-bis(3,5-dimethylpyrazolyl methyl)glycinate). These complexes were characterized by several techniques including X-ray crystallographic analysis, X-band electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry (ESI-MS), and cyclic voltammetry. The crystal structures of 1 and 3 revealed that both form infinite polymeric chains of Mn (II) complexes linked by the pendant carboxylate arms of the TCMA (-) and the BPZG (-) ligands in a syn-antipattern. Complex 2 crystallizes as a mononuclear Mn (II) cation, six-coordinate in a distorted octahedral geometry. Although complexes 1 and 3 crystallize as polymeric chains, all compounds present the same N3O-donor set atoms around the metal center as observed in the crystallographically characterized OxDC and OxOx. Moreover, complex 2 also contains two water molecules coordinated to the Mn center as observed in the active site of OxDC and OxOx. ESI-MS spectrometry, combined with EPR, were useful techniques to establish that complexes 1- 3 are present as mononuclear Mn (II) species in solution. Finally, complexes 1- 3 are able to model the resting state active sites, with special attention focused on complex 2 which provides the first exact first coordination sphere ligand structural model for the resting states of both OxDC and OxOx. 相似文献
86.
Neville SM Leita BA Halder GJ Kepert CJ Moubaraki B Létard JF Murray KS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(32):10123-10133
Three analogous one dimensional (1D) polymeric iron(II) spin crossover (SCO) materials containing the new ligand 4,6-bis(2',2'-pyridyl)pyrazine (bdpp) have been comprehensively characterised magnetically (thermal and light-induced) and structurally. Within this series are two polymorphs of the formula [Fe(NCS)(2)(bdpp)], 1 and 2 a, which differ magnetically in that phase 1 undergoes a full two-step SCO (T(1/2(1))=135 K and T(1/2(2))=90 K) whereas phase 2 a remains high spin (HS) over all temperatures. The central distinction between these two materials lies in the presence of intermolecular pi-pi interactions generated by the crystal packing in 1, which are absent in 2 a. The isostructural selenocyanate analogue of 2 a, [Fe(NCSe)(2)(bdpp)], 2 b, undergoes a full two-step SCO (T(1/2(1))=200 K and T(1/2(2))=125 K). Structural analyses of 1 and 2 b at a range of temperatures provide deep insight into their two-step SCO nature. Structural analysis of 1 at 25 K (1(LS-LS)), 123 K (1(LS-HS)) and 250 K (1(HS-HS)) reveals two distinct iron(II) centres at each temperature, with ordered, alternating HS and LS (low spin) sites at the intermediate plateau (IP) temperatures. In contrast, structural analysis of 2 b at 90 K (2 b(LS)), 150 K (2 b(LS/HS)) and 250 K (2 b(HS)) reveals one unique iron(II) centre at each temperature with an "averaged" LS/HS character at the IP temperature. Weak planes of diffuse scattering in the single-crystal X-ray diffraction patterns were observed for this phase at 90 and 150 K, indicating that 1D long range ordering of alternating HS/LS iron(II) centres occurs along the 1D coordination chains, but that there is no correlation between chains. The lack of observable diffuse scattering at 250 K suggests that the onset of the 1D structural ordering in the chain direction corresponds to the first step of the SCO and that this structural transition is electronically driven. The photomagnetic properties of both 1 and 2 b have been investigated and show approximately 62 and 53 % photo-excitation of a HS metastable state at low temperatures and T(LIESST) values of 55 and 49 K, respectively. Relaxation studies on the HS fraction in 2 b fitted well to a stretched exponential model with kinetic parameters indicative of weak cooperativity. 相似文献
87.
88.
O-GlcNAcylation of serine and threonine residues is a dynamic and essential post-translational modification involved in signaling pathways in eukaryotes. Studies of O-GlcNAcylation would be aided by small-molecule inhibitors of O-GlcNAc transferase (OGT), the sole enzyme know to mediate this modification, but discovery of such molecules has been hampered by poor expression of cloned OGT and lack of suitable high-throughput screens. This Communication describes the development an expression system to access large amounts of the catalytic domain of OGT and the implementation of a fluorescence-based substrate analogue displacement assay that has led to the discovery of a set of OGT inhibitors. This work lays the foundation for both structural and functional analysis of the catalytic domain of OGT. 相似文献
89.
Leclaire J Dagiral R Fery-Forgues S Coppel Y Donnadieu B Caminade AM Majoral JP 《Journal of the American Chemical Society》2005,127(45):15762-15770
The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers. 相似文献
90.