全文获取类型
收费全文 | 443篇 |
免费 | 22篇 |
国内免费 | 14篇 |
专业分类
化学 | 367篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 36篇 |
物理学 | 66篇 |
出版年
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 12篇 |
2020年 | 19篇 |
2019年 | 9篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 15篇 |
2015年 | 15篇 |
2014年 | 8篇 |
2013年 | 18篇 |
2012年 | 40篇 |
2011年 | 51篇 |
2010年 | 24篇 |
2009年 | 23篇 |
2008年 | 31篇 |
2007年 | 23篇 |
2006年 | 28篇 |
2005年 | 24篇 |
2004年 | 25篇 |
2003年 | 27篇 |
2002年 | 17篇 |
2001年 | 3篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 8篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1990年 | 2篇 |
1986年 | 1篇 |
1984年 | 6篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1979年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有479条查询结果,搜索用时 15 毫秒
1.
Multicomponent Na2V6O16.3H2O (barnesite) single-crystalline nanobelts were synthesized by a direct reaction-crystallization growth of bulk V2O5 and NaF powders under hydrothermal treatment without using any templates or catalysts. This new strategy could be extended to prepare other one-dimensional multicomponent nanomaterials including ammonium, alkali-metal or alkali-earth metal vanadium oxide bronzes and other transition metal oxyfluorides. This is an efficient and mild solution method with clear advantages over the traditional high-temperature approach for the large-scale production of 1D multicomponent nanomaterials. The applicability of this approach toward the preparation of other inorganic systems, such as tungstates and molybdates, will be explored. 相似文献
2.
We have successfully developed a new one-pot solution-phase route, namely microwave-assisted hydrothermal reduction/carbonization (MAHRC), for a rapid synthesis of coaxial Ag/C nanocables. The nanocables can self-assemble in situ in an end-to-end fashion into interconnected chains. 相似文献
3.
Kohli BM Eng JK Nitsch RM Konietzko U 《Rapid communications in mass spectrometry : RCM》2005,19(5):589-596
In liquid chromatography/tandem mass spectrometry (LC/MS/MS) analyses of complex peptide mixtures, dynamic exclusion functions are used to minimize repeat selections of identical precursors for collision induced dissociation (CID). We describe a new algorithm for the dynamic exclusion of m/z values during LC/MS/MS. Full-scan based peak exclusion (Fulspec) uses a simplified model of chromatographic peak formation to detect and exclude contaminants present throughout the run or that lead to broad peaks. Therefore, instead of excluding peptides from fragment analysis according to a rigidly predefined time window, the chromatographic properties of the detected analytes are used. The algorithm was tested on two datasets derived from previously published experiments. Fulspec achieves a distribution of CID spectra with minimal tailing on the retention time axis, without resorting to rigid exclusion of m/z values. The procedure further excludes intensities with a bias towards low-quality CID spectra. This combination frees up valuable analytical capacity. The underlying intensity vs. quality analyses challenge the assumption that abundant precursors automatically give the best identifications. Further validation of the algorithm will require its incorporation by equipment manufacturers into the instrument control programs. 相似文献
4.
This paper reports a new method for preconcentration and separation of trace amounts of molybdenum in seawater samples prior to determination by inductively coupled plasma–atomic emission spectroscopy (ICP–OES). Diethylenetriaminetetraacetic acid-functionalized polysiloxane (DETAP) was synthesized by carboxymethylation of amino groups on triamine immobilized polymer, which was prepared by modification of 3-chloropropylpolysiloxane with diethylenetriamine. The resulting polysiloxane is highly selective and efficient in chelating Mo(VI) at trace levels. It can be used as a column packing material. The polysiloxane column can be reused over ten times without losing its original properties, so it is suitable for preconcentration of molybdenum species in seawater samples before determination. The parameters governing the characteristics of polysiloxane for adsorption of Mo(VI) were investigated. These include the effect of pH, amount of polysiloxane, equilibrium time, adsorption isotherm, maximum adsorption capacity, interfering ions, flow rate, capacity for reuse, and desorption. The precision of the preconcentration method, calculated as the relative standard deviation of seawater samples, was 3%. The preconcentration factor was 100. The detection limit, defined as 3 times the standard deviation of five replicate measurements of the blank sample at pH 3, was 0.17 g L–1. Measurement results for standard reference materials were in good agreement with the certified values [(CRMs), NASS-2 Seawater (Open Ocean) and CASS-2 Seawater (Coastal)]. 相似文献
5.
Guillermina Burillo Takeshi Ogawa Jimmy S. Hwang 《Journal of polymer science. Part A, Polymer chemistry》1992,30(10):2159-2164
A number of diacetylene containing acrylate and methacrylates have been synthesized and the interaction between their propagating radicals and the diacetylene groups was studied by ESR spectroscopy. In the case of polymerization at 70°C using AIBN as an initiator, the propagating radicals of methacrylates are temporarily trapped with the diacetylenes with rapid exchange of the electron, thus showing strong signals of the propagating radicals. Gamma irradiation of the frozen state produces a blue color in samples, and the ESR signals were found to be those of uninteracted acrylate and methacrylates. From a comparison of spectral widths, there seems to exist an intramolecular interaction between the radicals and the diacetylene group at the frozen state. © 1992 John Wiley & Sons, Inc. 相似文献
6.
Supported iron tetrasulfophthalocyanine can efficiently catalyze the degradation of organic pollutants by H2O2 under visible light irradiation in an aqueous solution, and the catalyst can be easily recycled without apparent loss of activity. 相似文献
7.
Michael Woolman Jimmy Qiu Claudia M. Kuzan-Fischer Isabelle Ferry Delaram Dara Lauren Katz Fowad Daud Megan Wu Manuela Ventura Nicholas Bernards Harley Chan Inga Fricke Mark Zaidi Brad G. Wouters James T. Rutka Sunit Das Jonathan Irish Robert Weersink Howard J. Ginsberg David A. Jaffray Arash Zarrine-Afsar 《Chemical science》2020,11(33):8723
Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data. Spatially encoded pathology classifications are displayed at the site of laser sampling as color-coded pixels in an augmented reality video feed of the surgical field of view. This is enabled by two-way communication between surgical navigation and mass spectrometry data analysis platforms through a custom-built interface. Performance of the system was evaluated using murine models of human cancers sampled in situ in the presence of body fluids with a technical pixel error of 1.0 ± 0.2 mm, suggesting a 84% or 92% (excluding one outlier) cancer type classification rate across different molecular models that distinguish cell-lines of each class of breast, brain, head and neck murine models. Further, through end-point immunohistochemical staining for DNA damage, cell death and neuronal viability, spatially encoded PIRL-MS sampling is shown to produce classifiable mass spectral data from living murine brain tissue, with levels of neuronal damage that are comparable to those induced by a surgical scalpel. This highlights the potential of spatially encoded PIRL-MS analysis for in vivo use during neurosurgical applications of cancer type determination or point-sampling in vivo tissue during tumor bed examination to assess cancer removal. The interface developed herein for the analysis and the display of spatially encoded PIRL-MS data can be adapted to other hand-held mass spectrometry analysis probes currently available.Integration between a hand-held mass spectrometry desorption probe based on picosecond infrared laser technology (PIRL-MS) and an optical surgical tracking system demonstrates in situ tissue pathology from point-sampled mass spectrometry data. 相似文献
8.
Jimmy Orjala Anthony D. Wright Clemens A. J. Erdelmeier Otto Sticher Topul Rali 《Helvetica chimica acta》1993,76(4):1481-1488
Five New unusual monoterpene-substituted dihydrochalcones, the adunctins A–E (1″S)-1-{2′-hydroxy-4′-methoxy-6′-[4″-methyl-1″-(1?-methylethyl)cyclohex-3″ -en-1″ -yloxy]phenyl}-3-phenylpropan-1-one ( 1 ), (5aR*,8R*,9aR*)-3-phenyl-1-[5′,8′,9′,9′a-tetrahydro-3′-hydroxy-1′-methoxy-8′-(1″-methylethyl)-5′-a-methyldibenzo-[b,d]furan-4′-yl]propan-1-one ( 2 ), (2′R*,4″S*)-1-{6′-hydroxy-4′-methoxy-4″-(1?-methylethyl)spiro[benzo[b]-furan-2′(3′H),1″ -cyclohex-2″ -en]-7′-yl}-3-phenylpropan-1-one ( 3 ), (2′R*,4″R*)-1-{6′-hydroxy-4′-methylethyl-4″-(1?-methylethyl)spiro[benzo[b]furan-2′(3′H),1″-cyclohex-2″-en]-7′-yl}-3-phenypropan-1-one ( 4 ), and (5′aR*,6′S*, 9′R*,9′aS*)-1-[5′a,6′,7′,8′,9′a-hexahydro-3′,6′-methoxy-6′-methyl-9′-(1″-methylethyl)dibenzo[b,d]-furan-4′-yl]-3-phenylpropan-1-one ( 5 ) were isolated from the leaves of Piper aduncum (Piperaceae) by preparative liquid chromatography. In addition, (?)-methyllindaretin ( 6 ), trans-phytol, and α-tocopherol ( = vitamin E) were also isolated and identified. The structures were elucidated by spectroscopic methods, including 1D- and 2D-NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The antibacterial and cytotoxic potentials of the isolates were also investigated. 相似文献
9.
A novel solid-phase extraction (SPE) procedure for trace aromatic compounds in water samples has been developed using 12 aromatic compounds as model compounds and GC-MS and UV spectrophotometry for detection. The method is based on the fact that β-cyclodextrin (β-CD) epichlorohydrin (ECH) copolymer (β-CDEP) can extract non-ionized aromatic compounds quantitatively from aqueous samples. The polymer used is a colorless, transparent and insoluble solid with a maximum capacity of 0.82 μmol aromatic compounds per gram. It was synthesized by co-polymerization of β-CD and ECH and characterized by FT-IR and UV. β-CDEP does not contain double bonds, and therefore it does not have appreciable absorbance in the UV region. The optimum pH range for the extraction of aromatic compounds is 2.5-5.0. The method has high extraction efficiency with the recoveries between 90 and 101% for aromatic compounds at 0.02-1.67 ppm levels, and the analytes can be easily eluted by methanol washing after preconcentration. 相似文献
10.
Caroline K. Williams Amir Lashgari Nilakshi Devi Marcus Ang Ashwin Chaturvedi Pranita Dhungana Prof. Jianbing Jimmy Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6240-6246
In this work, the electrocatalytic reduction of dichloromethane (CH2Cl2) into hydrocarbons involving a main group element-based molecular triazole-porphyrin electrocatalyst H2PorT8 is reported. This catalyst converted CH2Cl2 in acetonitrile to various hydrocarbons (methane, ethane, and ethylene) with a Faradaic efficiency of 70 % and current density of −13 mA cm−2 at a potential of −2.2 V vs. Fc/Fc+ using water as a proton source. The findings of this study and its mechanistic interpretations demonstrated that H2PorT8 was an efficient and stable catalyst for the hydrodechlorination of CH2Cl2 and that main group catalysts could be potentially used for exploring new catalytic reaction mechanisms. 相似文献