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131.
A simple, fast, sensitive and robust analytical method using gas chromatography (GC)-isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled analogue d4-1,4-dichlorobenzene (d4-p-DCB) as internal standard (IS). Validation of the method was performed in two different GC-MS systems, using quadrupole MS (QMS) and ion-trap MS (ITMS) detectors, with no statistically significant differences between two. Recoveries were better than 91% with percent relative standard deviations lower than 12%. The instrumental limits of detection were 1 μg kg−1 in the GC-ITMS system and 0.6 μg kg−1 in the GC-QMS system. The expanded uncertainty was estimated as 17% at the currently accepted “action level” of 10 μg kg−1. The method was applied to the analysis of 310 honey samples in an extensive national monitoring study. A quality control (QC) system applied during the assays has demonstrated a good performance and long-term stability over a period of more than 8 months of continuous operation. 相似文献
132.
Analysis of stable and radioactive isotopes from bone collagen provides useful information to archaeologists about the origin and age of bone artifacts. Isolation and analysis of single amino acids from the proteins can provide additional and more accurate information by removing contamination and separating a bulk isotope signal into its constituent parts. In this paper, we report a new method for the separation and isolation of underivatized amino acids from bone collagen, and their analysis by isotope ratio MS and accelerator MS. RP chromatography is used to separate the amino acids with nonpolar side chains, followed by an ion pair separation to isolate the remaining amino acids. The method produces single amino acids with little or no contamination from the separation process and allows for the measurement of accurate stable isotope ratios and pure samples for radiocarbon dating. 相似文献
133.
An on-line Hg reduction technique using stannous chloride as the reductant was applied for accurate and precise mercury isotope ratio determinations by multi-collector (MC)-ICP/MS. Special attention has been paid to ensure optimal conditions (such as acquisition time and mercury concentration) allowing precision measurements good enough to be able to significantly detect the anticipated small differences in Hg isotope ratios in nature. Typically, internal precision was better than 0.002% (1 RSE) on all Hg ratios investigated as long as approximately 20 ng of Hg was measured with a 10-min acquisition time. Introducing higher amounts of mercury (50 ng Hg) improved the internal precision to <0.001%. Instrumental mass bias was corrected using 205Tl/203Tl correction coupled to a standard-sample bracketing approach. The large number of data acquired allowed us to validate the consistency of our measurements over a one-year period. On average, the short-term uncertainty determined by repeated runs of NIST SRM 1641d Hg standard during a single day was <0.006% (1 RSD) for all isotope pairs investigated (202Hg/198Hg, 202Hg/199Hg, 202Hg/200Hg, and 202Hg/201Hg). The precision fell to <0.01% if the long-term reproducibility, taken over 11 months (over 100 measurements), was considered. The extent of fractionation has been investigated in a series of sediments subject to various Hg sources from different locations worldwide. The ratio 202Hg/198Hg expressed as δ values (per mil deviations relative to NIST SRM 1641d Hg standard solution) displayed differences from +0.74 to −4.00‰. The magnitude of the Hg fractionation per amu was constant within one type of sample and did not exceed 1.00‰. Considering all results (the reproducibility of Hg standard solutions, reference sediment samples, and the examination of natural samples), the analytical error of our δ values for the overall method was within ±0.28‰ (1 SD), which was an order of magnitude lower than the extent of fractionation (4.74‰) observed in sediments. This study confirmed that analytical techniques have reached a level of long-term precision and accuracy that is sufficiently sensitive to detect even small differences in Hg isotope ratios that occur within one type of samples (e.g., between different sediments) and so far have unequivocally shown that Hg isotope ratios in sediments vary within approximately 5‰. 相似文献
134.
Díaz Huerta V Fernández Sánchez ML Sanz-Medel A 《Analytical and bioanalytical chemistry》2006,384(4):902-907
Total determination and speciation analysis of Se in commercial and selenised Agaricus mushrooms have been performed to investigate the Se species naturally occurring in non-enriched mushrooms as well as those
present in specimens grown in a Se-enriched medium. Mushroom aqueous and enzymatic extracts have been analysed by three complementary
chromatographic separation mechanisms (size-exclusion, anion-exchange and reversed-phase) coupled to an inductively coupled
plasma mass spectrometer with an octopole reaction system. Post-column isotope dilution analysis has been used on-line with
the separations for quantification of the Se species eluted. The 78Se-to-77Se isotope ratio was monitored after adequate corrections for both total determinations and Se species quantitative speciation.
The results showed marked differences not only in total Se contents but also in Se species found in the two types of Agaricus mushrooms investigated. Selenomethionine was detected in both of them (free in commercial mushrooms and incorporated into
proteins in selenised ones) together with a number of unknown selenocompounds. 相似文献
135.
136.
The harmonic vibrational frequencies of the open, ring and superoxide isomers of sulfur dioxide are predicted with the coupled-cluster
including all single and double excitations (CCSD) and coupled cluster singles and doubles with perturbative connected triples
[CCSD(T)] methods. The reliability of the results is discussed and comparisons are made to the recent observations of the
matrix-isolated SOO molecule reported by Chen, Lee and Lee.
Received: 3 December 1996 / Accepted: 17 January 1997 相似文献
137.
Myoung-Kyu Oh Wonshik Choi Jin-Ho Jeon Moonjoo Lee Youngwoon Choi Sangbum Park Jai-Hyung Lee Kyungwon An 《Spectrochimica Acta Part B: Atomic Spectroscopy》2004,59(12):1919-1926
We report the first observation of hyperfine structures (HFSs) and isotope shifts (ISs) of Sm I in the range of 540–560 nm using an atomic beam resonance–fluorescence technique. The least square fitting was used to determine hyperfine constants in 4f55d6s2 and 4f66s6p of atomic samarium (Sm I). The isotope shifts of 18 transition lines were also determined and analyzed by the King plot. 相似文献
138.
Koichi Miyai Masanori Nakamura Katsutoshi Tamura Sachio Murakami 《Journal of solution chemistry》1997,26(10):973-988
Excess enthalpy, excess isobaric heat capacity, density, and speed of sound in mixtures of heavy water (D2O) + dimethylsulfoxide (DMSO), and D2O + dimethylformamide (DMF) were measured at 25‡C. The same properties of the mixtures of normal water + DMSO, and H2O + DMF were also measured to estimate isotope effects on the thermodynamic excess functions. Both DMSO and DMF are proton
acceptors and thus form hydrogen bonds with water. Large negative excess enthalpies and volumes of mixing and excess isentropic
compressibilities show that the hydrogen bonding structures of DMSO and DMF with water are stronger and more compact than
those in pure water. The excess heat capacity of DMSO-containing mixtures changes sign from negative to positive with increasing
water content. The deviations of the excess properties of D2O systems from those of H2O systems indicate that the hydrogen bonding structure with D2O is stronger and more compact. 相似文献
139.
The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained.This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements).The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample. 相似文献
140.
Inagaki K Takatsu A Kuroiwa T Nakama A Eyama S Chiba K Okamoto K 《Analytical and bioanalytical chemistry》2004,378(5):1271-1276
Two types of sediment reference material (NMIJ 7302-a and 7303-a) for trace elements analysis have been prepared and certified by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original materials were collected from a bay near industrial activity in Kyushu (NMIJ CRM 7302-a; marine sediment) and from Lake Biwa (NMIJ CRM 7303-a; lake sediment). The sediment materials were air-dried, sieved, homogenized, packaged in 1000 glass bottles (60 g each), and radiation sterilized. Certification of these CRM for trace elements was conducted by NMIJ, where each element was determined by at least two independent analytical techniques. Isotope-dilution inductively coupled plasma mass spectrometry (ICP–MS) was applied for certification of all the elements except mono-nuclide elements such as As and Co. Other techniques such as ICP–MS with quadrupole mass spectrometry and sector-field mass spectrometry, inductively coupled plasma atomic emission spectrometry (ICP–AES), and atomic absorption spectrometry (AAS), were also used. Certified values have been provided for 14 elements (Sb, As, Cd, Cr, Co, Cu, Pb, Hg, Mo, Ni, Se, Ag, Sn, and Zn) in both CRM. 相似文献