全文获取类型
收费全文 | 1370篇 |
免费 | 26篇 |
国内免费 | 7篇 |
专业分类
化学 | 957篇 |
晶体学 | 2篇 |
力学 | 14篇 |
数学 | 174篇 |
物理学 | 256篇 |
出版年
2023年 | 5篇 |
2021年 | 15篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 18篇 |
2017年 | 5篇 |
2016年 | 11篇 |
2015年 | 22篇 |
2014年 | 16篇 |
2013年 | 47篇 |
2012年 | 70篇 |
2011年 | 97篇 |
2010年 | 54篇 |
2009年 | 50篇 |
2008年 | 88篇 |
2007年 | 89篇 |
2006年 | 88篇 |
2005年 | 93篇 |
2004年 | 75篇 |
2003年 | 63篇 |
2002年 | 63篇 |
2001年 | 25篇 |
2000年 | 33篇 |
1999年 | 20篇 |
1998年 | 20篇 |
1997年 | 18篇 |
1996年 | 24篇 |
1995年 | 20篇 |
1994年 | 9篇 |
1993年 | 19篇 |
1992年 | 12篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 4篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 20篇 |
1980年 | 13篇 |
1979年 | 13篇 |
1978年 | 9篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 16篇 |
1974年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有1403条查询结果,搜索用时 0 毫秒
71.
We study the solvation of iodide in water using density functional theory based molecular-dynamics simulations. Detailed analysis of the structural and dynamical properties of the first solvation shell is presented, showing a disruptive influence of the ion on the local water structure. Iodide-water hydrogen bonding is weak, compared to water-water hydrogen bonds. This effective repulsive ion-water interaction leads to the formation of a quite unstructured solvation shell. The dynamics of water molecules surrounding the iodide is relatively fast. The intramolecular structural and electronical properties of water molecules around the ion are not affected. 相似文献
72.
Patrick J. M. Stals Jeffrey C. Everts Robin de Bruijn Ivo A. W. Filot Maarten M. J. Smulders Rafael Martín‐Rapún Dr. Evgeny A. Pidko Dr. Tom F. A. de Greef Dr. Anja R. A. Palmans Dr. E. W. Meijer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):810-821
N‐Centred benzene‐1,3,5‐tricarboxamides (N‐BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid‐state behaviour and self‐assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X‐ray diffraction revealed that the chiral N‐BTA derivatives with branched 3,7‐dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Colho. In contrast, N‐BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable‐temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N‐BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N‐BTAs revealed a cooperative self‐assembly behaviour of the N‐BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants‐and‐soldiers as well as the majority‐rules principles were operative in stacks of N‐BTAs. In fact, the self‐assembly of N‐BTAs resembles closely that of their carbonyl (C?O)‐centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self‐assembly of N‐ and C?O‐BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N‐BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the Ph? NH bond compared to the Ph? CO bond and the diminished magnitude of dipole–dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N‐BTAs and C?O BTAs. 相似文献
73.
ten Cate AT Kooijman H Spek AL Sijbesma RP Meijer EW 《Journal of the American Chemical Society》2004,126(12):3801-3808
Bifunctional 2-ureido-4[1H]-pyrimidinone (UPy) derivatives can form small cyclic oligomers as well as long supramolecular polymers in chloroform solutions using the quadruple hydrogen-bonding motif. Ring-chain equilibria of a set of supramolecular monomers containing methyl-substituted alkyl linkers between the hydrogen-bonding UPy moieties were investigated by (1)H NMR spectroscopy and viscometry. The data were characterized in terms of critical concentration (CC, denoting the onset of polymerization) and equilibrium cyclic dimer concentration (EDC, representing preorganization of the monomer toward selective formation of cyclic dimer). Methyl substituents in the monomer were found to promote conformations favorable for cyclic dimerization, leading to an increase in both the EDC and the CC with respect to unsubstituted monomer. Furthermore, we observed an odd-even effect in the CC and EDC with increasing length of the linker between the hydrogen-bonding units. The combined results allow tuning of the critical concentration over a broad range and offer detailed information on the correlation between monomer structure, conformation, and polymerizability which may provide new insights for the study and design of other ring-chain equilibria or helix-random coil transitions. 相似文献
74.
PA Korevaar C Schaefer TF de Greef EW Meijer 《Journal of the American Chemical Society》2012,134(32):13482-13491
The influence of the ratio between poor and good solvent on the stability and dynamics of supramolecular polymers is studied via a combination of experiments and simulations. Step-wise addition of good solvent to supramolecular polymers assembled via a cooperative (nucleated) growth mechanism results in complete disassembly at a critical good/poor solvent ratio. In contrast, gradual disassembly profiles upon addition of good solvent are observed for isodesmic (non-nucleated) systems. Due to the weak association of good solvent molecules to monomers, the solvent-dependent aggregate stability can be described by a linear free-energy relationship. With respect to dynamics, the depolymerization of π-conjugated oligo(p-phenylene vinylene) (OPV) assemblies in methylcyclohexane (MCH) upon addition of chloroform as a good solvent is shown to proceed with a minimum rate around a critical chloroform/MCH solvent ratio. This minimum disassembly rate bears an intriguing resemblance to phenomena observed in protein unfolding, where minimum rates are observed at the thermodynamic midpoint of a protein denaturation experiment. A kinetic nucleation-elongation model in which the rate constants explicitly depend on the good solvent fraction is developed to rationalize the kinetic traces and further extend the insights by simulation. It is shown that cooperativity, i.e., the nucleation of new aggregates, plays a key role in the minimum polymerization and depolymerization rate at the critical solvent composition. Importantly, this shows that the mixing protocol by which one-dimensional aggregates are prepared via solution-based processing using good/poor solvent mixtures is of major influence on self-assembly dynamics. 相似文献
75.
Microbial adhesion to poly(ethylene oxide) brushes: influence of polymer chain length and temperature 总被引:1,自引:0,他引:1
Roosjen A van der Mei HC Busscher HJ Norde W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):10949-10955
Glass surfaces were modified by end-grafting poly(ethylene oxide) (PEO) chains having molecular weights of 526, 2000, or 9800 Da. Characterization using water contact angles, ellipsometry, and X-ray photoelectron spectroscopy confirmed the presence of the PEO brushes on the surface with estimated lengths in water of 2.8-, 7.5-, and 23.7-nm, respectively. Adhesion of two bacterial (Staphylococcus epidermidis and Pseudomonas aeruginosa) and two yeast (Candida albicans and Candida tropicalis) strains to these brushes was studied and compared to their adhesion to bare glass. For the bacterium P. aeruginosa and the yeast C. tropicalis, adhesion to the 2.8-nm brush was comparable to their adhesion on bare glass, whereas adhesion to the 7.5- and 23.7-nm brushes was greatly reduced. For S. epidermidis, adhesion was only slightly higher to the 2.8-nm brush than that to the longer brushes. Adhesion of the yeast C. albicans to the PEO brushes was lower than that to glass, but no differences in adhesion were found between the three brush lengths. After passage of an air bubble, nearly all microorganisms adhering to a brush were removed, irrespective of brush length, whereas retention of the adhering organisms on glass was much higher. No significant differences were found in adhesion nor retention between experiments conducted at 20 and those conducted at 37 degrees C. 相似文献
76.
Daniel Tordera Andreas M. Bünzli Antonio Pertegás Dr. José M. Junquera‐Hernández Prof. Edwin C. Constable Dr. Jennifer A. Zampese Prof. Catherine E. Housecroft Prof. Enrique Ortí Dr. Henk J. Bolink 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8597-8609
A new approach to obtain green‐emitting iridium(III) complexes is described. The synthetic approach consists of introducing a methylsulfone electron‐withdrawing substituent into a 4‐phenylpyrazole cyclometalating ligand in order to stabilize the highest‐occupied molecular orbital (HOMO). Six new complexes have been synthesized incorporating the conjugate base of 1‐(4‐(methylsulfonyl)phenyl)‐1 H‐pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light‐emitting electrochemical cells (LECs), green electroluminance is observed. High efficiencies and luminances are obtained at low driving voltages. This approach for green emitters is an alternative to the widely used fluorine‐based substituents in the cyclometalating ligands and opens new design possibilities for the synthesis of green emitters for LECs. 相似文献
77.
Xianwen Lou Christianus M. A. Leenders Arthur H. A. M. van Onzen Ralf A. A. Bovee Joost L. J. van Dongen Jef A. J. M. Vekemans E. W. Meijer 《Journal of the American Society for Mass Spectrometry》2014,25(2):297-300
Tetrahydrofuran (THF) is one of the most frequently used solvents in the MALDI TOF MS analysis of synthetic compounds. However, it should be used with caution because a trace amount of 4-hydroxybutanal (HBA) might be generated and accumulated in THF during storage. Since only a tiny amount of analytes is required in MALDI MS measurements, a trace amount of HBA might have a significant effect on the MS results. It was found that HBA will quickly react with primary and secondary amino compounds, leading to false results about the sample composition with an extra series of ions with additional mass of 70 Da in between. The formation of HBA can be inhibited by butylated hydroxytoluene (BHT) antioxidant. Therefore, when THF is required as the solvent for sample preparation, it is strongly recommended to use a BHT-stabilized one, at least for the analysis of compounds with amino groups. Figure
? 相似文献
78.
Hanna Talacua Serge H. M. Sntjens Shraddha H. Thakkar Aurelie M. A. Brizard Lex A. van Herwerden Aryan Vink Geert C. van Almen Patricia Y. W. Dankers Carlijn V. C. Bouten Ricardo P. J. Budde Henk M. Janssen Jolanda Kluin 《Macromolecular bioscience》2020,20(7)
For in situ tissue engineering (TE) applications it is important that implant degradation proceeds in concord with neo‐tissue formation to avoid graft failure. It will therefore be valuable to have an imaging contrast agent (CA) available that can report on the degrading implant. For this purpose, a biodegradable radiopaque biomaterial is presented, modularly composed of a bisurea chain‐extended polycaprolactone (PCL2000‐U4U) elastomer and a novel iodinated bisurea‐modified CA additive (I‐U4U). Supramolecular hydrogen bonding interactions between the components ensure their intimate mixing. Porous implant TE‐grafts are prepared by simply electrospinning a solution containing PCL2000‐U4U and I‐U4U. Rats receive an aortic interposition graft, either composed of only PCL2000‐U4U (control) or of PCL2000‐U4U and I‐U4U (test). The grafts are explanted for analysis at three time points over a 1‐month period. Computed tomography imaging of the test group implants prior to explantation shows a decrease in iodide volume and density over time. Explant analysis also indicates scaffold degradation. (Immuno)histochemistry shows comparable cellular contents and a similar neo‐tissue formation process for test and control group, demonstrating that the CA does not have apparent adverse effects. A supramolecular approach to create solid radiopaque biomaterials can therefore be used to noninvasively monitor the biodegradation of synthetic implants. 相似文献
79.
George SJ Tomović Ž Schenning AP Meijer EW 《Chemical communications (Cambridge, England)》2011,47(12):3451-3453
Preferred handedness in the supramolecular chirality of self-assembled achiral oligo(p-phenylenevinylene) (OPV) derivatives is induced by chiral solvents and spectroscopic probing provides insight into the mechanistic aspects of this chiral induction through chiral solvation. 相似文献
80.
A. Van Baalen C.J. Groenenboom H.J. De Liefde Meijer 《Journal of organometallic chemistry》1974,74(2):245-253
The synthesis and the properties of the complexes Cp2TaCl2, Cp2M(allyl), Cp2M(1-methylallyl) and Cp2M(2-methylallyl) with M Nb, Ta are described. The complex Cp2TaCl2 has one unpaired electron per tantalum atom, while the allyl complexes are diamagnetic. The IR and PMR spectra indicate that the allyl group is π-bonded to the metal. The mass spectra of the complexes are discussed; the thermal stability of the Cp2Nb- and Cp2Ta-(allyl) complexes was investigated by differential thermal analysis. The properties of the niobium and tantalum complexes are compared with those of the corresponding titanium complexes. 相似文献