全文获取类型
收费全文 | 1018篇 |
免费 | 33篇 |
国内免费 | 2篇 |
专业分类
化学 | 905篇 |
晶体学 | 7篇 |
力学 | 8篇 |
数学 | 61篇 |
物理学 | 72篇 |
出版年
2023年 | 6篇 |
2022年 | 9篇 |
2021年 | 44篇 |
2020年 | 19篇 |
2019年 | 14篇 |
2018年 | 18篇 |
2017年 | 10篇 |
2016年 | 42篇 |
2015年 | 19篇 |
2014年 | 51篇 |
2013年 | 60篇 |
2012年 | 55篇 |
2011年 | 88篇 |
2010年 | 63篇 |
2009年 | 48篇 |
2008年 | 85篇 |
2007年 | 82篇 |
2006年 | 72篇 |
2005年 | 63篇 |
2004年 | 51篇 |
2003年 | 35篇 |
2002年 | 39篇 |
2001年 | 11篇 |
2000年 | 10篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 7篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1906年 | 2篇 |
排序方式: 共有1053条查询结果,搜索用时 531 毫秒
51.
52.
Tailoring the properties of electrospun PHBV mats: Co-solution blending and selective removal of PEO
Microstructure, surface topography, thermal and mechanical features of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) electrospun non-woven mats were modified, modulated and tailored through blending with different polyethylene oxide (PEO) amounts (20, 30 and 50% wt/wt). The optimal parameters of the soaking protocol for the selective removal of the sacrificial polymer were accurately identified by means of scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA) and differential scanning calorimetry (DSC). The complete PEO removal after soaking in H2O for 7 days with daily refreshment was confirmed. The resulting samples were only comprised of PHBV fibers characterized by a remarkable decrease of the average size with respect to the respective blends. Their surface topography was corrugated and rough and presented nodules, pits, nanopores, shallow and elongated nanostructured indents/grooves along the fiber axis. A remarkable reduction (>75%) of the tensile modulus (E) of electrospun PHBV mats (15–20 MPa) was obtained, maintaining comparable elongation at break (εmax) values (20–30%). 相似文献
53.
Rosário Monteiro Gil Faria Manuela Meireles Luísa Correia‐Sá Diana Teixeira Ana Faria Conceição Calhau Valentina F. Domingues Cristina Delerue‐Matos 《Biomedical chromatography : BMC》2012,26(12):1494-1501
Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid‐phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18‐E), benzenesulfonic acid modified silica cation exchanger (SA), poly(styrene‐divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C18‐E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries > 70% with standard deviations (SD) < 15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC‐MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′‐DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
54.
55.
Manuela F. Frasco Vicky Vamvakaki Nikos Chaniotakis 《Journal of nanoparticle research》2010,12(4):1449-1458
In this study, we report on a novel hybrid structure for the direct sensing of metal ions based on the use of CdSe quantum
dots functionalized with tetrapyridyl-substituted porphyrin, a cation-selective carrier. It is shown that the porphyrin ion
carrier coordinates to Cd atoms of the CdSe quantum dots through the Lewis basic pyridyl groups. The porphyrin-quantum dot
ligation allows for the direct communication between the porphyrin and the underlying CdSe quantum structure. The quantum
yield of CdSe is maintained despite the robust capping generated when the unmetallated porphyrins coordinate onto the quantum
dots. Upon coordination with zinc ions, this porphyrin capping is shown to strongly contribute to the increase in the fluorescence
efficiency of CdSe, via an activating interaction with the quantum dots surface. The results provide the grounds for the development
of highly sensitive and selective nano-optode sensing systems. 相似文献
56.
57.
58.
Walter Vastarella Livia Della Seta Amedeo Masci Jan Maly Manuela De Leo Ligia Maria Moretto 《International journal of environmental analytical chemistry》2013,93(10-11):701-714
Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated. 相似文献
59.
Adriaan M. H. van der Veen Hugo Ent Annarita Baldan Valnei S. da Cunha Romeu J. Daroda Brian Lang Michele Schantz Manuela Ulberth-Buchgraber Andrea Held Ruth Hearn Richard J. C. Brown Paul J. Brewer 《Accreditation and quality assurance》2013,18(1):41-50
The main objective of the reference materials for biofuel specifications (BIOREMA) project is the development of two test materials (one bio-ethanol material and one biodiesel material) with well-established reference values. Of a series of three papers, this part describes the material preparation, homogeneity study, stability study, and characterisation of the bio-ethanol material. The test material thus obtained was used in an interlaboratory comparison (ILC) to assess current practices and comparability amongst laboratories providing bio-ethanol testing services. Only 13 participants provided data, resulting in a small dataset for evaluation. Further, it appeared that for a number of laboratories, there was not sufficient material for the determination of all requested parameters. In most cases, as far as the data permit, it can be concluded that the consensus values (based on participant’s results) are in good agreement with the reference or the BIOREMA values (obtained by NMIs participating in the project). For three parameters, namely ethanol content, water content, and density, there is good agreement between the reference and consensus values. For these parameters, the reproducibility standard deviation is close to, or even smaller than, the expanded uncertainty associated with the reference value. A number of parameters show very poor reproducibility, for example, pHe, electrolytic conductivity, and acidity. The same applies to sodium and copper content, which are very low and therefore challenging parameters to measure accurately. The results of the ILC underpin the need for certified reference materials and demonstrate the requirement for more robust quality control to improve the precision and trueness of the results from testing laboratories. 相似文献
60.
Jinxiong Lin Dr. Friedrich Wossidlo. Dr. Nathan T. Coles Manuela Weber Dr. Simon Steinhauer Priv.-Doz. Dr. Tobias Böttcher Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(7):e202104135
A phosphinine-borane adduct of a Me3Si-functionalized phosphinine and the Lewis acid B(C6F5)3 has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B2H6 with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct ( 6 -B(C6F5)3) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me3Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts. 相似文献