全文获取类型
收费全文 | 844篇 |
免费 | 23篇 |
国内免费 | 21篇 |
专业分类
化学 | 821篇 |
晶体学 | 2篇 |
综合类 | 5篇 |
数学 | 1篇 |
物理学 | 59篇 |
出版年
2023年 | 3篇 |
2022年 | 11篇 |
2021年 | 18篇 |
2020年 | 11篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 19篇 |
2016年 | 12篇 |
2015年 | 22篇 |
2014年 | 16篇 |
2013年 | 89篇 |
2012年 | 42篇 |
2011年 | 34篇 |
2010年 | 30篇 |
2009年 | 48篇 |
2008年 | 44篇 |
2007年 | 56篇 |
2006年 | 64篇 |
2005年 | 66篇 |
2004年 | 47篇 |
2003年 | 27篇 |
2002年 | 24篇 |
2001年 | 16篇 |
2000年 | 20篇 |
1999年 | 13篇 |
1998年 | 16篇 |
1997年 | 17篇 |
1996年 | 18篇 |
1995年 | 12篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1992年 | 25篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1986年 | 5篇 |
1985年 | 2篇 |
排序方式: 共有888条查询结果,搜索用时 281 毫秒
51.
Xirong Huang Nianqin Jie Shuhua Han Wenjuan Zhang Jianping Huang 《Mikrochimica acta》1997,126(3-4):329-333
The coordination reactions of bromopyrogallol red (BPR) with tri- and hexavalent chromium in the presence of cetyltrimethylammonium bromide (CTAB) have been studied by absorption spectrometry. Results show that the reactions of Cr(VI) and Cr(III) with BPR in the absence or presence of CTAB have different temperature dependences. The reaction mechanism of Cr(VI) is that Cr(VI) is first reduced by BPR to Cr(III) and then the Cr(III) produced reacts with BPR. Based on the study on the coordination reactions and the effects of surfactants upon them, a simple, rapid, sensitive and accurate method for Cr speciation has been developed. Over the range of 0–8 g Cr(VI) or 0–12g Cr(III) per 25ml final volume, the calibration curve is linear with a detection limit of 3.5 × 10–7 mol/1 for Cr(VI) or 4.4 × 10–7 mol/1 for Cr(III). 相似文献
52.
Ondřej Linhart Alžběta Kolorosová-Mrázová Jan Kratzer Jakub Hraníček Václav Červený 《Analytical letters》2019,52(4):613-632
An ultraviolet-photochemical generator (UV-PVG) capable of post-column on-line transformation of both organic and inorganic mercury species to cold vapor (Hg0) with subsequent detection by quartz tube-atomic absorption spectrometry (QT-AAS) was developed. Mercury(II), methylmercury(I), ethylmercury(I), and phenylmercury(I) were successfully detected after separation by reversed-phase high-performance liquid chromatography (RP-HPLC). Two types of AAS detectors were compared. The first was a commonly used line-source instrument while the second was a high-resolution continuum source (HR-CS) AAS. The latter provided better limits of detection: 0.47?µg?L?1 for Hg(II), 0.84?µg?L?1 for methylmercury(I), 0.80?µg?L?1 for ethylmercury(I), and 2.0?µg?L?1 for phenylmercury(I). The repeatability at 30?μg?L?1 was 3.6%, 4.1%, 6.2%, and 4.5% for these species (n?=?10). These figures of merit were comparable with those reported for more sensitive atomic fluorescence spectrometry. Nine sample extraction procedures were investigated. Extraction by tetramethylammonium hydroxide and HCl at 75?°C was selected as the only method compatible with the proposed separation and detection steps providing high extraction efficiency and no changes in mercury speciation. The applicability of the proposed high-performance liquid chromatography–ultraviolet-photochemical vapor generation–quartz tube-atomic absorption spectrometry method was demonstrated using fish samples and certified reference materials (CRM) DOLT-4 (dogfish liver) and ERM-CE464 (tuna fish). The results were comparable to those obtained by a reference method based on L-cysteine extraction and high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) determination. 相似文献
53.
Capillary electrophoresis on-line coupled with hydride generation-atomic fluorescence spectrometry for speciation analysis of selenium 总被引:2,自引:0,他引:2
A new method for speciation analysis of two inorganic selenium species was developed by on-line coupling of capillary electrophoresis (CE) with hydride generation-atomic fluorescence spectrometry (HG-AFS) and on-line conversion of Se(VI) to Se(IV). Baseline separation of Se(VI) and Se(IV) was achieved by CE in a 50 cm x 75 microm inside diameter (ID) fused-silica capillary at -20 kV using a mixture of 15 mmol.L(-1) NaH2PO4 and 0.5 mmol.L(-1) cetyltrimethylammonium bromide (pH 7.5) as electrolyte buffer. Se(VI) was on-line reduced to Se(IV) by mixing the CE effluent with concentrated HCl. The precision (relative standard deviation, RSD, n=7) ranged from 0.7 to 1.3% for migration time, 6.4 to 3.7% for peak height response, and 5.9 to 6.1% for peak area for the two selenium species at the 500 microg.L(-1) (as Se) level. The detection limits were 33 and 25 microg.L(-1) (as Se) for Se(VI) and Se(IV), respectively. The recoveries of the two selenium species in five locally collected water samples ranged from 88 to 114%. The developed method was applied to speciation analysis of inorganic selenium species in spiked natural water samples. 相似文献
54.
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
55.
Aristidis N. Anthemidis George A. Zachariadis John A. Stratis 《Analytica chimica acta》2005,547(2):237-242
A simple and robust on-line sequential insertion system coupled with hydride generation atomic absorption spectrometry (HG-AAS) was developed, for selective As(III) and total inorganic arsenic determination without pre-reduction step. The proposed manifold, which is employing an integrated reaction chamber/gas-liquid separator (RC-GLS), is characterized by the ability of the successful managing of variable sample volumes (up to 25 ml), in order to achieve high sensitivity. Arsine is able to be selectively generated either from inorganic As(III) or from total arsenic, using different concentrations of HCl and NaBH4 solutions. For 8 ml sample volume consumption, the sampling frequency is 40 h−1. The detection limit is cL = 0.1 and 0.06 μg l−1 for As(III) and total arsenic, respectively. The precision (relative standard deviation) at 2.0 μg l−1 (n = 10) level is sr = 2.9 and 3.1% for As(III) and total arsenic, respectively. The performance of the proposed method was evaluated by analyzing the certified reference material NIST CRM 1643d and spiked water samples with various concentration ratios of As(III) to As(V). The method was applied for arsenic speciation in natural waters samples. 相似文献
56.
A method for direct de termination of total in organic arsenic (III+V), arsenic (III) and dimethylarsinate (DMA) in sea water was developed by combining continuous‐flow selective hydride generation and inductively coupled plasma mass spectrometry (ICP‐MS) is presented. The principle underlying selective hydride generation is based on proper control of the reaction conditions for achieving separation of the respective arsenic species. The effects of pH and composition of reaction media on mutual interference between the arsenic species were investigated in detail. The results indicate that the appropriate media for the selective determination of total in organic arsenic, DMA and As(III) are 6 M HNO3, acetate buffer at pH = 4.63 and citrate buffer at pH = 6.54, respectively. The concentrations of total inorganic arsenic species, As(III+V), and As(III) were respectively deter mined and that of As(V) was obtained by the difference between them. As to the concentration of DMA, it was obtained after correction from the interference caused by As(III) and As(V). By following the established procedure, the detection lim its (as based on 3‐sigma criterion) for As(III+V), As(III) and DMA were 0.050, 0.009, and 0.002 ng/mL, respectively. There liability of the pro posed method was evaluated in terms of precision and spike addition. The results indicated that the precision of better than 3% and spike recovery of 95 to 105% for all the arsenic species tested in the natural sea water samples can be obtained. 相似文献
57.
The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C18 column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H2O2-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH2OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH2OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel. 相似文献
58.
Speciation of Cr(III) and Cr(VI) can be attained by flow injection analysis with amperometric detection. Cr(VI) is reduced in an acidic medium to Cr(III) with a glassy carbon electrode at —0.1 V vs. Ag/AgCl and the current is recorded. Cr(III) is oxidised on-line to Cr(VI) with alkaline hydrogen peroxide solution. From the difference of the total chromium and Cr(VI), the amount of Cr(III) was obtained. A linear calibration curve for Cr(VI) was obtained for the concentration ranges 0.01-5.0ppm of Cr(VI) and we have calculated the limit of determination to be about 0.5ppb. We have studied the degree of reproducibility obtained using the solid electrodes under various conditions. The influence of flow rate, coil length, interfenences and the extent of reaction were studied. 相似文献
59.
M. Lachica E. Barahona 《International journal of environmental analytical chemistry》2013,93(1-4):219-221
Abstract The effect of using solution matrices in calibration standards different from those employed for the extraction steps in the determination of Cd, Cr, Cu, Ni and Zn were tested. Cu and Zn are little affected by matrix effects but, if the extractant is ammonium acetate, the use of other matrices may result in too high Cd, Cr and Ni values. 相似文献
60.
K. Wallmann M. Kersten J. Gruber U. Förstner 《International journal of environmental analytical chemistry》2013,93(1-4):187-200
Abstract The binding forms of Co, Cd, Cu, Pb, and Zn in an anoxic, sulfide-bearing sediment were investigated by performing both thermodynamic equilibrium calculations and sequential extractions. Care was taken to maintain oxygen-free conditions during the whole experiment. The calculations suggested that trace metals were bound to sulfidic minerals. Sequential extraction results, however, showed increased importance of exchangeable and reducible fractions in the order Cu < Cd < Pb < Zn < Co. Thermodynamic equilibrium calculations of the chemical reactions during extraction showed that Cd, Co, Pb, and Zn sulfides are to a significant extent soluble in the acetate-exchangeable (step 1 + 2) and oxalate-reducible (step 3) fractions. Neglecting the dissolution of sulfide minerals would lead to a misinterpretation of the experimental results. 相似文献