全文获取类型
收费全文 | 541篇 |
免费 | 21篇 |
国内免费 | 2篇 |
专业分类
化学 | 420篇 |
晶体学 | 6篇 |
力学 | 8篇 |
数学 | 59篇 |
物理学 | 71篇 |
出版年
2023年 | 6篇 |
2022年 | 3篇 |
2021年 | 12篇 |
2020年 | 15篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 6篇 |
2016年 | 20篇 |
2015年 | 23篇 |
2014年 | 24篇 |
2013年 | 47篇 |
2012年 | 36篇 |
2011年 | 46篇 |
2010年 | 25篇 |
2009年 | 15篇 |
2008年 | 24篇 |
2007年 | 28篇 |
2006年 | 31篇 |
2005年 | 29篇 |
2004年 | 25篇 |
2003年 | 17篇 |
2002年 | 15篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1986年 | 2篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1960年 | 1篇 |
1954年 | 1篇 |
1937年 | 1篇 |
1936年 | 1篇 |
1932年 | 2篇 |
排序方式: 共有564条查询结果,搜索用时 171 毫秒
21.
Hubert Schmidbaur Graham A. Bowmaker Ulrich Deschler Cornelia Dörzbach Rudolf Herr Beatrix Milewski-mahrla 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):167-170
Abstract Structural data of phosphorus ylides are summarized and discussed. Conformational preferences in solution and in the solid state, as followed by NMR spectroscopy and X-ray diffraction, indicate a strong gauche effect for the lone pairs of electrons at the ylidic carbon atom. One- and two-electron oxydation of ylide carbanions is accomplished with copper(II) as the oxidant, leading to oxidative coupling or to halogenation, respectively. 相似文献
22.
Estefanía Moreno-Gordaliza Sven J. van der Lee Ayşe Demirkan Cornelia M. van Duijn Johan Kuiper Petrus W. Lindenburg Thomas Hankemeier 《Analytica chimica acta》2016
A new capillary isotachophoresis (cITP) method for lipoprotein profiling with superior lipoprotein coverage compared to previous methods has been developed, resolving twice as many lipoprotein species (18 peaks/fractions) in serum or plasma in less than 9.5 min. For this, a novel mixture of 24 spacers, including amino acids, dipeptides and sulfonic acids, was developed and fine-tuned, using predictive software (PeakMaster) and testing of spiked serum samples. Lipoprotein peaks were identified by serum-spiking with reference lipoproteins. Compatibility with common lipophilic stains for selective lipoprotein detection with either UV/Vis or laser-induced fluorescence was demonstrated. A special new capillary with a neutral coating (combining water-compatible OV1701-OH deactivation and methylation) was used for the first time for electrodriven separations, allowing very stable separations in a pH 8.8–9.4 gradient system, being functional for more than 100 injections. Excellent reproducibility was achieved, with coefficients of variation lower than 2.6% for absolute migration times. Comparison was performed with human plasma samples analyzed by NMR, leading to similar results with cITP after multivariate statistics, regarding group-clustering and lipoprotein species correlation. The new cITP method was applied to the analysis of serum samples from a LDL receptor knock-out mice model fed either a normal diet or a western-type diet. Differences in the lipoprotein levels and in the sublipoprotein types were detected, showing a shift to more atherogenic particles due to the high cholesterol diet. In summary, this novel method will allow more detailed and informative profiling of lipoprotein particle subtypes for cardiovascular disease research. 相似文献
23.
Influence of the degree of ionization on the growth mechanism of poly(diallyldimethylammonium)/poly(acrylic acid) multilayers 下载免费PDF全文
Dörte Bütergerds Christian Kateloe Cornelia Cramer Monika Schönhoff 《Journal of Polymer Science.Polymer Physics》2017,55(5):425-434
pH‐dependent growth laws of the mass coverage Γ(n) of poly(diallyldimethylammonium) chloride and poly(acrylic acid) (PAA) layer‐by‐layer films are analyzed by Quartz Crystal Microbalance‐D. (Attenuated Total Reflection)‐FTIR spectroscopy shows a degree of dissociation of acrylic acid groups in the films identical to that in solution. Apart from pH‐regimes of differently pronounced exponential and linear growth, the corresponding kinetics indicate pH‐dependent adsorption, reorganization, and diffusion processes. As the thickest films form with almost uncharged PAA (low pH), the results can only partly be explained by the dissociation degree of PAA in the film. For intermediate and high pH values chain interdiffusion as a mechanism for nonlinear growth is strongly dependent on the charge density of the PAA chains. However, at low pH other types of interactions, most likely ion–dipole interactions, play a major role in the multilayer growth. Furthermore, a change in the symmetry of growth can be observed in the low to intermediate pH range. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 425–434 相似文献
24.
Uwe J. Meierhenrich Prof. Dr. Jean‐Jacques Filippi Dr. Cornelia Meinert Pierre Vierling Dr. Jason P. Dworkin Dr. 《Angewandte Chemie (International ed. in English)》2010,49(22):3738-3750
Recent major discoveries in membrane biophysics hold the key to a modern understanding of the origin of life on Earth. Membrane bilayer vesicles have been shown to provide a multifaceted microenvironment in which protometabolic reactions could have developed. Cell‐membrane‐like aggregates of amphiphilic molecules capable of retaining encapsulated oligonucleotides have been successfully created in the laboratory. Sophisticated laboratory studies on the origin of life now show that elongation of the DNA primer takes place inside fatty acid vesicles when activated nucleotide nutrients are added to the external medium. These studies demonstrate that cell‐like vesicles can be sufficiently permeable to allow for the intake of charged molecules such as activated nucleotides, which can then take part in copying templates in the protocell interior. In this Review we summarize recent experiments in this area and describe a possible scenario for the origin of primitive cells, with an emphasis on the elongation of encapsulated nucleotides. 相似文献
25.
The amination reactions of chloromethylated polystyrene with N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine were studied. The physical properties, particularly the solubility properties of the resulting polymers, are influenced by the hydrophobic properties of the long alkyl chain on the N+ atoms. The main factor that influences the kinetics of the reactions is the polymersolvent interaction parameter. 相似文献
26.
Sven Zukunft Martina Sorgenfrei Cornelia Prehn Gabriele Möller Jerzy Adamski 《Chromatographia》2013,76(19-20):1295-1305
Dried blood spot (DBS) samples are already successfully used in newborn screening and pharmacological analyses. The application of DBS matrix to further metabolomic methods will considerably extend the analytical options for the diagnostics of metabolic diseases. We present an MS/MS based method for the simultaneous extraction and quantification of 188 metabolites from dried blood spots. We provide a sensitive and reproducible method that adapts the AbsoluteIDQ? p180 kit of Biocrates to the DBS matrix for the quantification of metabolites of different substance classes including amino acids, biogenic amines, free carnitine, acylcarnitines, hexoses, glycerophospholipids, lysophosphatidylcholines, phosphatidylcholines, and sphingolipids. 相似文献
27.
Cornelia Stolle Bojidarka Ivanova Michael Spiteller 《Journal of inclusion phenomena and macrocyclic chemistry》2013,76(1-2):75-85
The experimental and theoretical spectroscopic and spectrometric elucidation in solid-state and gas-phase on the interacting ionic species of applied oriented synthetic derivatives on the base of the stilbazolium salts as molecular template was reported. The correlation between the molecular structure, and vibrational properties within THz-regime (10-0.3 THz) was performed. The collective vibrations, and gas-phase stabilized ionic species were comprehensive studied by the Raman spectroscopy and matrix-assisted laser desorption/ionization mass spectrometry, using the embedded organic dyes in host matrixes. The performed solid-state quantum chemical calculations contributed to further understanding of the nature of the guest–host interacting systems as well as to explain the observed optical phenomena within the THz-region. 相似文献
28.
Hermina Iulia Petkes Emese Gál Luiza Găină Mihaela Sabou Cornelia Majdik Luminiţa Silaghi-Dumitrescu 《Comptes Rendus Chimie》2014,17(10):1050-1056
The synthesis of new phenothiazinyl- and phenyl-nitrones under classical versus microwave heating conditions is described. Better yields were obtained under microwave irradiation in the condensation reactions of phenothiazyl-carbaldehyde with hydroxylamine derivatives. The structures of the new phenothiazinyl-nitrones were assigned on the basis of MS, FT–IR and NMR spectra. The new nitrones and some known phenyl-nitrones were screened for their antibacterial and antifungal activity against several Candida species, Gram negative bacteria, such as E. coli, Citrobacter spp, Morganella spp, Pseudomonas aeruginosa, Klebsiella pneumoniae (± ESBL), Proteus spp, Acinetobacter spp and the Gram positive bacterium Staphylococcus aureus, with moderate results. 相似文献
29.
Michael Esseling Annamaria Zaltron Wolfgang Horn Cornelia Denz 《Laser \u0026amp; Photonics Reviews》2015,9(1):98-104
This contribution presents an optofluidic droplet router which is able to route and steer microdroplets using optically induced forces created solely by the bulk photovoltaic effect on a nonlinear substrate. The combination of microfluidic tools with the properties of a photorefractive crystal allows for the generation of dielectrophoretic forces that can be either repulsive, leading to virtual barriers, or attractive, creating virtual rails. The sign of these forces is solely determined by the electrical properties of the liquid medium under investigation. Moreover, the induced structures on the bottom of the microfluidic channel are optically reconfigurable, so that the same device can easily be adopted for different purposes. Appropriate droplet‐generating devices are fabricated by UV illumination of SU‐8 and polydimethylsiloxane replica molding of the master structures. The bottom of the channels is formed by an iron‐doped lithium niobate crystal, whose internal electric fields are induced by structured illumination patterns and exert dielectrophoretic forces on droplets in the microfluidic section.
30.
Poor aqueous solubility of active compounds is a major issue in today’s drug delivery. In this study the smartFilm-technology was exploited to improve the dermal penetration efficacy of a poorly soluble active compound (curcumin). Results were compared to the dermal penetration efficacy of curcumin from curcumin bulk suspensions and nanocrystals, respectively. The smartFilms enabled an effective dermal and transdermal penetration of curcumin, whereas curcumin bulk- and nanosuspensions were less efficient when the curcumin content was similar to the curcumin content in the smartFilms. Interestingly, it was found that increasing numbers of curcumin particles within the suspensions increased the passive dermal penetration of curcumin. The effect is caused by an aqueous meniscus that is created between particle and skin if the dispersion medium evaporates. The connecting liquid meniscus causes a local swelling of the stratum corneum and maintains a high local concentration gradient between drug particles and skin. Thus, leading to a high local passive dermal penetration of curcumin. The findings suggest a new dermal penetration mechanism for active compounds from nano-particulate drug delivery systems, which can be the base for the development of topical drug products with improved penetration efficacy in the future. 相似文献