全文获取类型
收费全文 | 376篇 |
免费 | 12篇 |
专业分类
化学 | 226篇 |
晶体学 | 1篇 |
力学 | 12篇 |
数学 | 78篇 |
物理学 | 71篇 |
出版年
2023年 | 8篇 |
2021年 | 3篇 |
2020年 | 17篇 |
2019年 | 14篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 10篇 |
2015年 | 11篇 |
2014年 | 12篇 |
2013年 | 24篇 |
2012年 | 17篇 |
2011年 | 16篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 26篇 |
2007年 | 20篇 |
2006年 | 10篇 |
2005年 | 12篇 |
2004年 | 8篇 |
2003年 | 9篇 |
2002年 | 11篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1989年 | 5篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 5篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 6篇 |
1970年 | 2篇 |
1966年 | 2篇 |
1954年 | 2篇 |
1934年 | 2篇 |
排序方式: 共有388条查询结果,搜索用时 31 毫秒
61.
Jason E. Bara Evan S. Hatakeyama Christopher J. Gabriel Xiaohui Zeng Sonja Lessmann Douglas L. Gin Richard D. Noble 《Journal of membrane science》2008,316(1-2):186-191
Cross-linkable gemini room temperature ionic liquids (GRTILs) were synthesized and photo-cross-linked into thin films. The resultant polymer membranes were tested for their permeabilities to CO2, N2, CH4 and H2. Permeabilities for each gas were found to be much lower when compared to previously reported poly(RTIL) membranes, mainly as a result of highly restricted diffusion. Separation factors were similar to previously studied poly(RTIL) membranes. CH4 and N2 fluxes were small enough to consider these membranes as “barrier” films to the transport of those gases. Poly(GRTILs) may have use in applications where flow of those gases is not desirable. 相似文献
62.
Riedinger C Endicott JA Kemp SJ Smyth LA Watson A Valeur E Golding BT Griffin RJ Hardcastle IR Noble ME McDonnell JM 《Journal of the American Chemical Society》2008,130(47):16038-16044
In this study we present a method for defining the binding modes of a set of structurally related isoindolinone inhibitors of the MDM2-p53 interaction. This approach derives the location and orientation of isoindolinone binding, based on an analysis of the patterns of magnitude and direction of chemical shift perturbations for a series of inhibitors of the MDM2-p53 interaction. The MDM2-p53 complex is an attractive target for therapeutic intervention in cancer cells with intact tumor suppressor p53, as it offers the possibility of releasing p53 by blocking the MDM2-p53 binding site with a small molecule antagonist to promote apoptosis. Isoindolinones are a novel class of MDM2-antagonists of moderate affinity, which still require the development of more potent candidates for clinical applications. As the applicability of conventional structural methods to this system is limited by a number of fundamental factors, the exploitation of the information contained in chemical shift perturbations has offered a useful route to obtaining structural information to guide the development of more potent compounds. For a set of 12 structurally related isoindolinones, the data suggests 4 different orientations of binding, caused by subtle changes in the chemical structure of the inhibitors. 相似文献
63.
Carreon MA Li S Falconer JL Noble RD 《Journal of the American Chemical Society》2008,130(16):5412-5413
SAPO-34 membranes were prepared by in situ crystallization on alpha-Al2O3 porous supports. The crystal size of the seeds was effectively controlled in the 0.7 to 8.5 micron range by employing different structure-directing agents. Seeds smaller than 1 micron produced membranes with CO2/CH4 separation selectivities higher than 170 and unprecedented CO2 permeances as high as 2.0 x 10(-6) mol/m2.s.Pa at 295 K and a feed pressure of 224 kPa. The membranes effectively separated CO2/CH4 mixtures up to 1.7 MPa. 相似文献
64.
Axel Durand Zanna Chase Ashley T. Townsend Taryn Noble Emily Panietz Karsten Goemann 《International journal of environmental analytical chemistry》2016,96(2):119-136
Microwave-assisted digestion permits a rapid and total dissolution of sediments and various other sample types, allowing easier and more accurate multi-element determinations. In this study, we present an optimised microwave digestion method for the complete digestion of 200 mg of carbonate-rich sediments. The optimised method prevents the formation of precipitates and assures a complete dissolution of the material. The optimised method involves treatment with concentrated hydrochloric acid (HCl) prior to microwave digestion, which prevents the formation of an insoluble calcium fluoride precipitate associated with the use of hydrofluoric acid (HF). Three different certified reference samples along with a pure calcium carbonate standard and a carbonate-rich in-house marine sediment sample were considered. Sediments were found to only be partially digested if insufficient HF was present, while a noticeable fluoride-based precipitate was found if excess HF was present. Twenty elements were analysed using sector field inductively coupled plasma mass spectrometry (ICP-MS) (Al, Ag, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Na, Ni, Sr, Th, Ti, U, V and Zn). A total sample digestion with average elemental recoveries above 90% was obtained by reacting carbonate-rich samples with HCl on a hotplate at 150°C for 2 h (time for the total release of generated CO2), prior to any microwave digestion step. This extra step prevented the accumulation of gas in the sealed vessels during digestion, which would otherwise influence the carbonate chemical equilibria and make insoluble calcium available for precipitation. After this initial treatment, the improved digestion method consisted of microwave attack employing a mix of concentrated HCl, nitric acid (HNO3) and HF (4 mL/10 mL/2 mL), followed by evaporation on a hotplate. The limits of detection (LOD) obtained using the optimised microwave protocol and ICP-MS measurements were below 0.1 µg/kg for the trace elements and below 0.2 mg/kg for major elements. 相似文献
65.
Understanding Complex Electrochemical Impedance Spectroscopy in Corrosion Systems Using in‐situ Synchrotron Radiation Grazing Incidence X‐ray Diffraction
下载免费PDF全文
![点击此处可从《Electroanalysis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Muhammad Tanzirul Alam Emilyn Wai Lyn Chan Roland De Marco Yanliang Huang Stuart Bailey 《Electroanalysis》2016,28(9):2166-2170
The difficulty in interpreting electrochemical impedance spectroscopy (EIS) data has limited the potential of the method despite its utility as an electrochemical method for studies of electrode reactions and interfacial structures. Taking the test case of the carbon dioxide corrosion of carbon steel, in‐situ synchrotron radiation grazing incidence X‐ray diffraction (SR‐GIXRD) has been demonstrated to be a powerful technique for validating and understanding the interfacial structures associated with complex EIS data. Carbon dioxide corrosion was found to occur in several steps, which may only be surmised by EIS, but the use of SR‐GIXRD in conjunction with EIS has enabled the establishment of a link between EIS time constants and structural changes associated with the evolution of corrosion products with time. By comparison to previous studies by the authors and others in this field, this communication provides the first direct experimental evidence linking SR‐GIXRD surface compositional data to otherwise indistinctive EIS time constants. 相似文献
66.
Measurement uncertainty is a vital issue within analytical science. There are strong arguments that primary sampling should be considered the first and perhaps the most influential step in the measurement process. Increasingly, analytical laboratories are required to report measurement results to clients together with estimates of the uncertainty. Furthermore, these estimates can be used when pursuing regulation enforcement to decide whether a measured analyte concentration is above a threshold value. With its recognised importance in analytical measurement, the question arises of 'what is the most appropriate method to estimate the measurement uncertainty?'. Two broad methods for uncertainty estimation are identified, the modelling method and the empirical method. In modelling, the estimation of uncertainty involves the identification, quantification and summation (as variances) of each potential source of uncertainty. This approach has been applied to purely analytical systems, but becomes increasingly problematic in identifying all of such sources when it is applied to primary sampling. Applications of this methodology to sampling often utilise long-established theoretical models of sampling and adopt the assumption that a 'correct' sampling protocol will ensure a representative sample. The empirical approach to uncertainty estimation involves replicated measurements from either inter-organisational trials and/or internal method validation and quality control. A more simple method involves duplicating sampling and analysis, by one organisation, for a small proportion of the total number of samples. This has proven to be a suitable alternative to these often expensive and time-consuming trials, in routine surveillance and one-off surveys, especially where heterogeneity is the main source of uncertainty. A case study of aflatoxins in pistachio nuts is used to broadly demonstrate the strengths and weakness of the two methods of uncertainty estimation. The estimate of sampling uncertainty made using the modelling approach (136%, at 68% confidence) is six times larger than that found using the empirical approach (22.5%). The difficulty in establishing reliable estimates for the input variable for the modelling approach is thought to be the main cause of the discrepancy. The empirical approach to uncertainty estimation, with the automatic inclusion of sampling within the uncertainty statement, is recognised as generally the most practical procedure, providing the more reliable estimates. The modelling approach is also shown to have a useful role, especially in choosing strategies to change the sampling uncertainty, when required. 相似文献
67.
Method validation was conducted for an enzyme-linked immunosorbent assay (ELISA) for the determination of domoic acid (DA) toxins, known to give amnesic shellfish poisoning (ASP) symptoms, in shellfish. The calibration curve range of the assay is approximately 10-260 pg/mL, with a dynamic working range for DA toxins in shellfish from 0.01 to at least 250 mg/kg. The ASP ELISA showed no significant cross-reactivity to structural analogs, and proved to be robust to deliberate alterations of the optimal running conditions. The shellfish matrix effects observed with mussels, oysters, and scallops were eliminated by diluting shellfish extracts 1:200 prior to analysis, leading to a limit of detection at 0.003 mg/kg. Thirteen blank shellfish homogenates were spiked with certified mussel material containing DA to levels in the range of 0.1-25 mg DA/kg, and analyzed in quadruplicate on 3 different days. The relative standard deviation (RSD) under intra-assay repeatability conditions ranged from 6.5 to 13.1%, and under interassay repeatability conditions the RSD ranged from 5.7 to 13.4%, with a mean value of 9.3%. The recoveries ranged from 85.5 to 106.6%, with a mean recovery of 102.2%. A method comparison was conducted with liquid chromatography with ultraviolet detection, using naturally contaminated scallop samples (n = 27) with DA levels at 0-244 mg/kg. The overall correlation coefficient was 0.960 and the slope of the regression was 1.218, indicating a good agreement between the methods. 相似文献
68.
Sargunam Caleb Noble Chandar Kannappan Santhakumar Mahadevimangalam Narayanasamy Arumugham 《Transition Metal Chemistry》2009,34(8):841-848
Twelve surfactant Schiff base ligands were synthesized from salicylaldehyde and its chloro-, bromo- and methoxy- derivatives
by condensation with long-chain aliphatic primary amines, and a number of mixed ligand cobalt(III) surfactant Schiff base
coordination complexes of the type [Co(trien)A]2+ were synthesized from the corresponding dihalogeno complexes by ligand substitution. The Schiff bases and their complexes
were characterized by physico-chemical and spectroscopic methods. The complexes form foams in aqueous solution upon shaking.
The critical micelle concentration (CMC) values of the complexes in aqueous solution were obtained from conductance measurements.
Specific conductivity data (at 303–323 K) served for the evaluation of the thermodynamics of micellization (
\Updelta G\textm0 \Updelta G_{\text{m}}^{0} ,
\Updelta H\textm0 \Updelta H_{\text{m}}^{0} ,
\Updelta S\textm0 \Updelta S_{\text{m}}^{0} ). The complexes were tested for its antimicrobial activity. 相似文献
69.
Mathew A. Johnson Pascal Noble L. Miguel Rodrigues Kevin Zumbrun 《Archive for Rational Mechanics and Analysis》2013,207(2):669-692
In a companion paper, we established nonlinear stability with detailed diffusive rates of decay of spectrally stable periodic traveling-wave solutions of reaction diffusion systems under small perturbations consisting of a nonlocalized modulation plus a localized (L 1) perturbation. Here, we determine time-asymptotic behavior under such perturbations, showing that solutions consist of a leading order of a modulation whose parameter evolution is governed by an associated Whitham averaged equation. 相似文献
70.
Blake Barker Mathew A. Johnson Pascal Noble L. Miguel Rodrigues Kevin Zumbrun 《Applied Mathematics Letters》2012,25(5):824-829
In this note, we announce a general result resolving the long-standing question of nonlinear modulational stability, or stability with respect to localized perturbations, of periodic traveling-wave solutions of the generalized Kuramoto–Sivashinsky equation, establishing that spectral modulational stability, defined in the standard way, implies nonlinear modulational stability with sharp rates of decay. The approach extends readily to other second- and higher-order parabolic equations, for example, the Cahn Hilliard equation or more general thin film models. 相似文献