全文获取类型
收费全文 | 3509篇 |
免费 | 308篇 |
国内免费 | 657篇 |
专业分类
化学 | 3552篇 |
晶体学 | 63篇 |
力学 | 64篇 |
综合类 | 20篇 |
数学 | 37篇 |
物理学 | 738篇 |
出版年
2024年 | 5篇 |
2023年 | 70篇 |
2022年 | 99篇 |
2021年 | 91篇 |
2020年 | 116篇 |
2019年 | 115篇 |
2018年 | 101篇 |
2017年 | 161篇 |
2016年 | 145篇 |
2015年 | 153篇 |
2014年 | 183篇 |
2013年 | 320篇 |
2012年 | 244篇 |
2011年 | 275篇 |
2010年 | 224篇 |
2009年 | 322篇 |
2008年 | 291篇 |
2007年 | 277篇 |
2006年 | 229篇 |
2005年 | 185篇 |
2004年 | 186篇 |
2003年 | 116篇 |
2002年 | 116篇 |
2001年 | 83篇 |
2000年 | 84篇 |
1999年 | 59篇 |
1998年 | 46篇 |
1997年 | 43篇 |
1996年 | 26篇 |
1995年 | 19篇 |
1994年 | 23篇 |
1993年 | 15篇 |
1992年 | 18篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1976年 | 1篇 |
排序方式: 共有4474条查询结果,搜索用时 31 毫秒
101.
We have evaluated the potential of near-infrared spectroscopy (NIRS) as a technique for rapid analysis of lactate in whole blood. To test the NIRS technique, a comparison was made with a standard clinical method using whole blood samples taken from five exercising human subjects at three different stage of exercise. To expand lactate concentration within the physiological range, standard additions method was used to generate 45 unique data points. Spectra were collected over the 2050-2400 nm spectral range with a 1 mm optical path length quartz cell. Reference lactate concentrations in the samples were determined by enzymatic measurements. Estimates and calibration of the lactate concentration with NIRS was made using partial least squares (PLS) regression analysis and leave-N-out cross validation on second derivative spectra. Separate calibrations were determined from each of the subject samples and cumulative PRESS was used to determine the number of PLS factors in the final model. The results from the PLS model presented are generated from the five individual calibration coefficient vectors and provided a correlation coefficient of 0.978 and a standard error of cross validation of 0.65 mmol l−1 between the enzymatic assay and the NIRS technique. To study the parameters that impact the spectra baseline and the correlation between the calculated model and the data, referenced measurements of lactate against baseline spectrum were made for each individual. A correlation coefficient of 0.992 and a standard error of cross validation of 0.21 mmol l−1 were found. The results suggest that NIRS may provide a valuable tool to assess physiological status for both research and clinical needs. 相似文献
102.
Jim Ho 《Analytica chimica acta》2002,457(1):125-148
Biological aerosol detection in real time is an urgent civilian and military requirement. Such detection capability will be useful in environmental monitoring, for example, in gathering information in perceived hazardous areas such as housing developments downwind of sewage treatment plants. To be truly functional, the instrument has to operate continuously, 24 h a day and 7 days a week with minimal maintenance and few false alarms. A novel concept is proposed. The system employs a rapid front-end warning/alarming mechanism based on optical technologies that provides useful information for protection decision makers. This is connected to a sample collector that feeds a slower back-end liquid chemistry system that provides analytical results to the medical personnel to assist in prophylaxis and therapy decisions. Experience gained from measuring fluorescence signals of single bacterial spores under flow cytometry (FCM) using UV excitation at 340-360 nm, was applied to concept testing of a prototype instrument, built to do the same for aerosols. This machine was capable of resolving particle size as well as fluorescence intensity of each particle under laboratory and field conditions; it was called the fluorescent aerodynamic particle sizer (FLAPS). This paper describes practical aspects of measuring biological aerosols when the results must be compared to reference samplers that provide culturable or “live” data. Treatment of particle size and fluorescence information is discussed with respect to FLAPS and reference data fidelity. Along with an objective method to evaluate FLAPS data correlation to reference data, an approach for determining limit of detection in the field is discussed. In addressing the back-end detector chemistry, we have prioritized a number of important biological characteristics that must be given to a clinician to help in prophylaxis and therapy decisions. A series of biochemical measurements are proposed to define the threat of a sample and different solutions are given to implement these tests. We predict that the future for biological detection looks promising for fluorescence in situ hybridization (FISH) techniques in identifying microorganisms. A conceptual instrument based on merging FCM and microchip-based analysis is described. 相似文献
103.
制备了对丙烯直接气相环氧化具有较好催化性能的Ag-MoO3催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯+氧气的混合气在Ag和Ag-MoO3催化剂表面上的吸附及反应行为. 研究表明, 丙烯在Ag和Ag-MoO3催化剂表面上吸附后, 均不发生化学反应, 而环氧丙烷吸附后在较高温度下则发生开环和聚合反应直至产生积炭. 与Ag催化剂相比, 在Ag-MoO3催化剂上, MoO3的加入在降低催化剂活性的同时, 在一定程度上抑制了产物环氧丙烷的开环及深度反应, 使环氧丙烷的选择性提高. 另外, 在较低的反应温度和较短的滞留时间下, 环氧丙烷发生深度反应的程度明显降低. 相似文献
104.
通过原子转移自由基聚合方法, 在丁酮/异丙醇混合溶剂中合成了分子量可控和分布较窄的聚丙烯酸叔丁酯-b-聚N-异丙基丙烯酰胺(PtBA-b-PNIPAM)嵌段共聚物, 用GPC和 1 H NMR对其结构进行了表征. PtBA-b-PNIPAM在甲苯中水解得到聚丙烯酸-b-聚N-异丙基丙烯酰胺(PAA-b-PNIPAM). 用动态光散射技术对PAA-b-PNIPAM在水溶液中的自组装行为随pH值和温度变化的响应进行了初步研究. 相似文献
105.
表面引发原子转移自由基聚合方法合成Fe3O4/PMMA复合纳米微粒 总被引:7,自引:1,他引:7
采用表面引发原子转移自由基聚合方法合成了核壳结构的磁性高分子纳米微粒. 作为聚合反应引发剂的3-氯丙酸, 首先与油酸修饰的Fe3O4纳米微粒表面的部分油酸置换, 然后在Fe3O4纳米微粒表面引发甲基丙烯酸甲酯聚合, 合成的纳米复合材料用TEM, FTIR, XRD和DSC表征. 磁性测试结果表明, 所制备的磁性高分子纳米微粒仍具有超顺磁性, 但由于聚合物的存在, 其饱和磁化强度降低. 相似文献
106.
107.
Phosphate selective electrodes have been produced based upon rubbery membranes containing heterocylic macrocycles as sensors covalently bound to a cross-linked polystyrene-block–polybutadiene-block–polystyrene (SBS) polymer. The membranes were robust and the best HPO42−-selective membrane fabricated was composed of 7.1% (m/m) dicumyl peroxide, 28.3% (m/m) 2-nitrophenyloctylether, 9.8% (m/m) 3-(10-undecenyl)-1,5,8-triazacyclodecane-2,4-dione, 31.0% (m/m) SBS and 23.8% (m/m) PoleStar™ 200R (clay-based filler). The characteristics of this electrode were a linear Nernstian range of 3.9×10−3 to 1×10−6 mol dm−3 HPO42− with a limit of detection of 1.0×10−6 mol dm−3 HPO42−, a slope of −29.7±0.9 mV per activity decade and a pH range from 6 to 8. Selectivity coefficients for phosphate against various interfering anions (chloride, sulfate and nitrate) were determined. Response times were 2 min or under, stability of response and electrode lifetime in continuous use were also very satisfactory. The response behavior of HPO42−-ISEs based upon mobile and bound ionophores was comparable and suggests that mobility of the ionophore is not necessary to obtain a working ISE and that covalent binding of ionophores can be used to produce ISEs of increased stability and robustness. 相似文献
108.
Bianca S. Shemper A. Ersin Acar Lon J. Mathias 《Journal of polymer science. Part A, Polymer chemistry》2002,40(3):334-343
The copper‐catalyzed atom transfer radical polymerization (ATRP) of poly(propylene glycol) methacrylate (PPGM) in solution to produce linear and starlike polymers is reported, using methylethyl ketone as the solvent and a temperature of 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer without protecting hydroxyl end groups of monomer. The polymerizations were consistent with “living” or controlled processes, as revealed by the linear evolution of molecular weight with conversion. Increasing the [M]0:[I]0 ratio resulted in increasing molecular weights, whereas the polydispersity indices remained low (Mw/Mn < 1.4) even at high conversion. Decreasing the [CuBr]0:[I]0 ratio resulted in lower conversions, slightly larger polydispersities, and decreased molecular weights, likely resulting from a lower initiation efficiency. Polymers were characterized by 1H and 13C NMR; molecular weights of polymers with low degrees of polymerization were estimated by end‐group analysis from 13C NMR spectra obtained using distortionless enhancement by polarization transfer and the gated decoupling techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 334–343, 2002 相似文献
109.
Hiroyoshi Nakajima Katsuhiro Yamada Yuki Iseki Satoru Hosoda Ayako Hanai Yasunori Oumi Toshiharu Teranishi Tsuneji Sano 《Journal of polymer science. Part A, Polymer chemistry》2003,41(24):3324-3332
Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C4H9)3 catalyst. The cross polarization/magic angle spinning (CP/MAS) 13C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N2 adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (Mw) and molecular weight distribution (Mw/Mn) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (Mw = 200,000–450,000, Mw/Mn = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003 相似文献
110.
Metal speciation measurement by diffusive gradients in thin films technique with different binding phases 总被引:1,自引:0,他引:1
Since its invention in the mid-1990s, the diffusive gradients in thin films (DGT) technique has rapidly become one of the most promising in situ sampling techniques for trace metal measurement in natural waters. We investigated here the possibility of using DGT devices with different binding phases to determine different DGT labile fractions of Cd and Cu in laboratory solutions and in natural waters. Several binding phases were studied, including conventional Chelex 100 resin imbedded polyacrylamide hydrogel (Chelex) and several recently developed binding phases, poly(acrylamide-co-acrylic acid) (PAM-PAA) gel, poly(acrylamidoglycolic acid-co-acrylamide) (PAAG-PAM) gel, Whatman P81 cellulose phosphate ion-exchange membrane (P81), and poly(4-styrenesulfonate) (PSS) aqueous solution. Laboratory testing in metal solutions spiked with EDTA or humic acid suggested that all the DGT devices measured only free metal ions and inorganic metal complexes. Upon field testing at both freshwater and seawater sites it was found that the DGT labile metal concentrations measured by different binding phases can be significantly different, suggesting that the DGT labile metal fractions were dependent on binding strength of the binding phase. By designing binding phases that can compete with different natural water complexing ligands to varying extents, it is possible to use these different DGT devices to measure metal speciation in natural waters. 相似文献