全文获取类型
收费全文 | 1596篇 |
免费 | 211篇 |
国内免费 | 324篇 |
专业分类
化学 | 1628篇 |
晶体学 | 32篇 |
力学 | 5篇 |
综合类 | 20篇 |
数学 | 1篇 |
物理学 | 445篇 |
出版年
2024年 | 4篇 |
2023年 | 25篇 |
2022年 | 54篇 |
2021年 | 64篇 |
2020年 | 75篇 |
2019年 | 69篇 |
2018年 | 68篇 |
2017年 | 64篇 |
2016年 | 66篇 |
2015年 | 59篇 |
2014年 | 91篇 |
2013年 | 141篇 |
2012年 | 112篇 |
2011年 | 117篇 |
2010年 | 74篇 |
2009年 | 80篇 |
2008年 | 80篇 |
2007年 | 109篇 |
2006年 | 72篇 |
2005年 | 67篇 |
2004年 | 66篇 |
2003年 | 60篇 |
2002年 | 58篇 |
2001年 | 66篇 |
2000年 | 55篇 |
1999年 | 53篇 |
1998年 | 40篇 |
1997年 | 36篇 |
1996年 | 27篇 |
1995年 | 33篇 |
1994年 | 31篇 |
1993年 | 22篇 |
1992年 | 21篇 |
1991年 | 16篇 |
1990年 | 11篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有2131条查询结果,搜索用时 812 毫秒
61.
The solvatochromic behavior of a penta‐tert‐butyl prydinium N‐phenolate betaine dye was studied using UV‐visible spectrophotometry in several binary mixture solvents. The solvent polarity parameter, ET (1) (kcal. mol?1) was calculated from the position of the longest‐wavelength intramolecular charge transfer absorption band of this penta‐tert‐butyl betaine dye. For binary solvent mixtures, all plots of ET (1) versus the mole fraction of a more polar component are nonlinear owing to preferential solvation of the probe by one component of the binary solvent mixture. In the computation of ET (1) it was assumed that the two solvents mixed interact to form a common structure with an ET (1) value not always intermediate between those of the two solvents mixed. The results obtained are explained by the strong synergism observed for some of the binary mixtures with strong hydrogen bond donors (HBD) solvents such as alcohols. 相似文献
62.
The monomer-dimer equilibrium of an asymmetric cyanine dye has been investigated by means of UV-Vis spectroscopy. The data have been processed by a recently developed chemometric method for quantitative analysis of undefined mixtures, that is based on simultaneous resolution of the overlapping bands in the whole set of absorption. In this work the dimerization constant of 1-carboxydecyl-4-{3-[3-methyl-3H-benzothiazol-2-ylidene]-propenyl}-quinolinium (TO-3) has been determined by studying the dependence of absorption spectrum on temperature in the range 25-72.5 °C at different total concentrations of dye (8.5×10−6 to 2.87×10−5 M). Utilizing the van’t Hoff relation, which describes the dependence of the equilibrium constant on temperature, as constraint we determine the spectral responses of the monomer and dimer species as well as the enthalpy and entropy of the dimerization equilibrium. 相似文献
63.
64.
The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium
was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair,
lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization
rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization
with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid
chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to
reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results
showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent
with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the
cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence
of ferrous ion was also necessary together with the lactate and sulfate substrates. 相似文献
65.
Tetraallylsilane was functionalised using (chloromethyl)dimethylsilane to give the first generation chloromethyl terminated dendrimer 1. The resulting dendrimer was successfully reacted with K[CpM(CO)2] (Cp=η5-C5H5; M=Fe, Ru) to give Si[(CH2)3SiMe2CH2MCp(CO)2]4 functionalised dendrimers in satisfactory yield. Reaction of dendrimer 1 with NaI in acetone gave the -SiMe2CH2I functionalised dendrimer, while reactions of 1 with K[CpM(CO)3] (M=Mo, W, Re), Li[C5Me4H], Na[C5Me4H], the cobaloxime nucleophile or tert-BuLi were not successful. 相似文献
66.
Christian K. Riener Andreas Ebner Alex A. Gall Yuri L. Lyubchenko Hermann J. Gruber 《Analytica chimica acta》2003,479(1):59-75
We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG800 diamine was glutarylated, the mono-adduct NH2-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy. 相似文献
67.
We described reversible affinity interactions of antibody molecules at a chemically functionalized electrode surface for a repeatedly renewable affinity-biosensing interface. Underlying biofunctionalizable monolayers were constructed with poly(amidoamine) dendrimers, whose surface chain-end groups were double-functionalized with biotinyl ligand and ferrocenyl groups for biospecific recognition and electron transfer reactions, respectively. Functionalized monolayers on gold electrodes provide platform surfaces for biospecific recognition reaction with monoclonal anti-biotin antibody molecules. Bound antibody molecules were dissociated from the surface via displacement reaction by the addition of free biotin in solution, enabling the affinity surface to be renewed and repeatedly utilized. Tracking of the association/dissociation reaction cycles were performed by registering the bioelectrocatalytic currents at the electrode using glucose oxidase (GOx) as a signal generator and ferrocenyl-tethered dendrimer (Fc-D) as an electron transferring mediator in electrolyte. Shielding of the affinity surface by biospecifically bound antibody molecules caused hindrance in electron transfer, resulting in reduced signal from cyclic voltammetry. By the displacement reaction using free biotin, bound antibody molecules were dissociated from the surface and the bioelectrocatalytic signal was restored. With the affinity surfaces constructed in this work, continuous association/dissociation reactions have been successfully accomplished, providing a possibility of reusable affinity biosensing interface. 相似文献
68.
The effect of surface condition on the photoalignment of light-induced methyl red (MR) adsorption phenomena on various substrates based on azo dye-doped liquid crystals is investigated. The results show that the polar surface energy determines the initiation of MR adsorption phenomena. The surface polarity energy of different substrates, which are modulated by oxygen plasma treatment (OPT), is further examined using the sessile drop method. The results also indicate that the uniformity and efficiency of MR adsorption can be enhanced by OPT. Light intensity influences the MR adsorption rate. The uniformity of MR adsorption onto various substrates is analysed via polarised optical microscopy. 相似文献
69.
Dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles as a novel recyclable catalyst for N‐arylation of nitrogen heterocycles and green synthesis of 5‐substituted 1H‐tetrazoles 下载免费PDF全文
In this study, dendrimer‐encapsulated Cu(Π) nanoparticles immobilized on superparamagnetic Fe3O4@SiO2 nanoparticles were prepared via a multistep‐synthesis. Then, the synthesized composite was fully characterized by various techniques such as fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), dynamic light scattering (DLS), UV‐vis spectroscopy, energy dispersive X‐ray analysis (EDX), thermogravimetric analysis (TGA) and vibration sample magnetometer (VSM). From the information gained by FE‐SEM and TEM studies it can be inferred that the particles are mostly spherical in shape and have an average size of 50 nm. Also, the amount of Cu is determined to be 0.51 mmol/g in the catalyst by inductively coupled plasma (ICP) analyzer. This magnetic nano‐compound has been successfully applied as a highly efficient, magnetically recoverable and stable catalyst for N‐arylation of nitrogen heterocycles with aryl halides (I, Br) and arylboronic acids without using external ligands or additives. The catalyst was also employed in a one‐pot, three‐component reaction for the efficient and green synthesis of 5‐substituted 1H‐tetrazoles using various aldehydes, hydroxylamine hydrochloride and sodium azide in water. The magnetic catalyst can be easily separated by an external magnet bar and is recycled seven times without significant loss of its activity. 相似文献
70.
A novel methodology was implemented in the present study to concurrently control power conversion efficiency (η) and durability (D) of co-sensitized dye solar cells. Applying response surface methodology (RSM) and Desirability Function (DF), the main influential assembling (dye volume ratio and anti-aggregation agent concentration) and operational (performance temperature) parameters were systematically changed to probe their main and interactive effects on the η and D responses. Individual optimization based on RSM elucidated that D can be solely controlled by changing the ratio of vat-based organic photosensitizers, whereas η takes both effects of dye volume ratio and anti-aggregation concentration into account. Among the studied factors, the performance temperature played the most vital role in η and D regulation. In particular, however, multi-objective optimization by DF explored the degree to which one should be careful about manipulation of assembling and operational parameters in the way maximization of performance of a co-sensitized dye solar cell. 相似文献