全文获取类型
收费全文 | 1235篇 |
免费 | 31篇 |
国内免费 | 2篇 |
专业分类
化学 | 1016篇 |
晶体学 | 22篇 |
力学 | 4篇 |
数学 | 108篇 |
物理学 | 118篇 |
出版年
2023年 | 12篇 |
2022年 | 17篇 |
2021年 | 55篇 |
2020年 | 31篇 |
2019年 | 33篇 |
2018年 | 22篇 |
2017年 | 23篇 |
2016年 | 48篇 |
2015年 | 41篇 |
2014年 | 46篇 |
2013年 | 116篇 |
2012年 | 87篇 |
2011年 | 79篇 |
2010年 | 52篇 |
2009年 | 60篇 |
2008年 | 53篇 |
2007年 | 65篇 |
2006年 | 63篇 |
2005年 | 47篇 |
2004年 | 51篇 |
2003年 | 36篇 |
2002年 | 28篇 |
2001年 | 20篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 14篇 |
1997年 | 8篇 |
1996年 | 7篇 |
1995年 | 15篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 9篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1962年 | 2篇 |
排序方式: 共有1268条查询结果,搜索用时 203 毫秒
41.
Ewa Bulska Katarzyna Wróbel Adam Hulanicki 《Fresenius' Journal of Analytical Chemistry》1992,342(9):740-743
Summary The optimal conditions for the determination of aluminium and chromium in blood serum are proposed. Several sample pretreatment procedures for the purpose are compared. The best results are obtained by sample dilution with nitric acid (0.1 mol/l) and addition of Mg(NO3)2 as modifier with a magnesium concentration of 0.2 mg/ml. This procedure has been used for studying the intestinal intake of aluminium by patients after oral administration of aluminium compounds. 相似文献
42.
This paper reviews derivatisation processes applied in chromatographic determination of acidic herbicides (with carboxyl and phenol groups), mainly in aqueous environmental samples. The discussion focuses on the basic derivatisation reactions used to convert herbicides to derivatives to make them analysable by gas chromatography, and possibly to reduce detection limits and/or increase extraction recovery from aqueous samples. The reactions are transesterification, esterification, silylation, alkylation, and extractive and pyrolytic alkylation. The reagents used to conduct the reactions are numerous. Diazomethane is a very efficient methylation reagent but explosive and toxic. Methyl iodide also ensures rapid and efficient methylation. Benzyl bromide can be used directly in water but derivatisation yield is low and reproducibility is poor. Butyl chloroformate and dimethyl sulfite can also be used for derivatisation in water, and acetic anhydride can be used for in-situ derivatisation of phenolic herbicides. For increasing selectivity of GC detection pentafluorobenzyl bromide (for ECD) and (2-cyanethyl)dimethyl(diethylamino)silane (for NPD) have been applied. Very characteristic ions are produced in mass spectra if silyl groups are introduced, e.g. by using bis(trimethylsilyl)trifluoroacetamide. Tetramethylammonium, trimethylphenylammonium, tetraalkylammonium, and trimethylsulfonium hydroxides and salts can by used for derivatisation at elevated temperature in the GC injection port. Extractive alkylation is relatively efficient if tetraalkylammonium salts with long chain alkyl groups are used. 相似文献
43.
Izabela Jendrzejewska Tomasz Goryczka Ewa Pietrasik Joanna Klimontko Josef Jampilek 《Molecules (Basel, Switzerland)》2020,25(24)
Studies carried out by X-ray and thermal analysis confirmed that acetaminophen (paracetamol), declared by the manufacturers as an Active Pharmaceutical Ingredient (API), was present in all studied medicinal drugs. Positions of diffraction lines (2θ angles) of the studied drugs were consistent with standards for acetaminophen, available in the ICDD PDF database Release 2008. values were lower than 0.2°, confirming the authenticity of the studied drugs. Also, the values of interplanar distances dhkl for the examined samples were consistent with those present in the ICDD. Presence of acetaminophen crystalising in the monoclinic system (form I) was confirmed. Various line intensities for API were observed in the obtained diffraction patterns, indicating presence of the preferred orientation of the crystallites in the examined samples. Thermal analysis of the studied substances confirmed the results obtained by X-ray analysis. Drugs containing only acetaminophen as an API have melting point close to that of pure acetaminophen. It was found that presence of other active and auxiliary substances affected the shapes and positions of endothermal peaks significantly. A broadening of endothermal peaks and their shift towards lower temperatures were observed accompanying an increase in the contents of additional substances being “impurities” in relation to the API. The results obtained by a combination of the two methods, X-ray powder diffraction (XRPD) and differential scanning calorimetry/thermogravimetry (DSC/TGA), may be useful in determination of abnormalities which can occur in pharmaceutical preparations, e.g., for distinguishing original drugs and forged products, detection of the presence of a proper polymorphic form or too low content of the active substance in the investigated drug. 相似文献
44.
Małgorzata Pazderska-Szabłowicz Agnieszka Białkowska Ewa Kita 《Transition Metal Chemistry》2006,31(3):413-420
New chromium(III) complexes, [Cr(C2O4)2(2-hnic)]2− and [Cr(C2O4)2(3-hpic)]2− (where 2-hnic = O,O′-bonded 2-hydroxynicotinic acid and 3-hpic = N,O-bonded 3-hydroxypicolinic acid), were obtained and characterized
in solution. The acid-catalyzed aquation of the both complexes leads to liberation of the appropriate pyridinecarboxylic acid
and formation of cis-[Cr(C2O4)2(H2O)2]−. Kinetics of these reactions were studied spectrophotometrically in the 0.1–1.0 M HClO4 range, at I = 1.0 M. In the case of [Cr(C2O4)2(2-hnic)]2−, a slow chelate-ring opening at the Cr–O (phenolate) bond is followed by a fast Cr–O (carboxylate) bond breaking. The rate
law: kobs = kHQH[H+] was established, where kH is the acid-catalyzed rate constant and QH is the protonation constant of the coordinated phenolate oxygen atom. In the case of [Cr(C2O4)2(3-hpic)]2−, the reversible chelate-ring opening at Cr–N bond is followed by the rate determining step – the one-end bonded ligand liberation.
The rate law for the first step was determined: kobs = k1+k−1/Q1[H+], where k1 and k−1 are the rate constants of the chelate-ring opening and closure and Q1 is the protonation constant of the pyridine nitrogen atom. The aquation mechanisms are proposed and the effect of ligand
coordination mode on complex reactivity is discussed. 相似文献
45.
A series of homoleptic complexes of hexacoordinate cobalt(II) and copper(II) complexes with 3,5-disubstituted homo- and heteroscorpionate tris(pyrazolyl)borate anionic ligands (Tp′) were synthesized, i.e. bis[hydrotris(3-phenyl,5-methylpyrazol-1-yl)borato]cobalt(II), bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) and bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]copper(II) and their structures were elucidated crystallographically. The complexes were also formed spontaneously during attempted metathesis of the corresponding Tp′M(NCS) complexes into Tp′M(OOCCH(OH)CH3) complexes. In the case of the analogous conversion applied for the thiocyanato [hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3,5-dimethylpyrazol-1-yl)boratocobalt(II) complex with sodium carboxylates (lactate, pyruvate and 2-hydroxybutyrate), the cross-transfer of pyrazolyl residues between starting anionic ligands was observed resulting in formation of bis-ligand homo- and heteroleptic Tp′CoTp″ complexes, where Tp′, Tp″ were tris(pyrazolyl)borates composed of n 3(5)-phenyl,5(3)-methylpyrazolyl and (3−n) 3,5-dimethylpyrazolyl residues (n=0–3) identified by mass spectrometry. Metathesis of thiocyanate in thiocyanato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) into pyruvate led to the isolation of stable the pyruvato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) complex, the structure of which was determined crystallographically. The Tp′ ligands are η3 coordinated to metal ions in every case, whereas the pyruvate anion is coordinated through carboxylate and carbonyl oxygen atoms to the cobalt center. Two rotational isomers distinguishable by 1H NMR spectroscopy for the hexacoordinate bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) complex were detected in solution. 相似文献
46.
Expanding the Scope of Hypervalent Iodine Reagents for Perfluoroalkylation: From Trifluoromethyl to Functionalized Perfluoroethyl 下载免费PDF全文
Dr. Václav Matoušek Jiří Václavík Peter Hájek Julie Charpentier Zsófia E. Blastik Ewa Pietrasiak Alena Budinská Prof. Dr. Antonio Togni Dr. Petr Beier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):417-424
A series of new hypervalent iodine reagents based on the 1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole and 1,2‐benziodoxol‐3‐(1H)‐one scaffolds, which contain a functionalized tetrafluoroethyl group, have been prepared, characterized, and used in synthetic applications. Their corresponding electrophilic fluoroalkylation reactions with various sulfur, oxygen, phosphorus, and carbon‐centered nucleophiles afford products that feature a tetrafluoroethylene unit, which connects two functional moieties. A related λ3‐iodane that contains a fluorophore was shown to react with a cysteine derivative under mild conditions to give a thiol‐tagged product that is stable in the presence of excess thiol. Therefore, these new reagents show a significant potential for applications in chemical biology as tools for fast, irreversible, and selective thiol bioconjugation. 相似文献
47.
48.
Joanna Bryś Magdalena Wirkowska Agata Górska Ewa Ostrowska-Ligęza Andrzej Bryś Piotr Koczoń 《Journal of Thermal Analysis and Calorimetry》2013,112(1):481-487
The aim of this paper was to assess the oxidative stability of structured lipids synthesized by enzymatic interesterification of a blend of lard and rapeseed oil with concentrates of n ? 3 fatty acids. Differential scanning calorimetry was used to evaluate the oxidation induction time of interesterified fats as a parameter assessing resistance of tested fats to their thermal-oxidative decomposition. Moreover, the IR spectra registered in the classic spectral range (4000–400 cm?1) were used to differentiate the samples of interesterified fats. The results show that the interesterification process decreased the induction time. Increased content polar fraction in the interesterified fatty product can reduce its resistance to oxidation. FT-IR data of selected spectral ranges correlate with the value of induction time at a statistically significant level. This is a proof that chemical changes occurring during different treatments of the starting mixture can be monitored by FT-IR spectroscopy. Moreover, obtained correlations can be used for the evaluation of an induction value of an unknown oil sample. 相似文献
49.
50.
Magdalena Wirkowska Ewa Ostrowska-Lig?za Agata Górska Piotr Koczoń 《Journal of Thermal Analysis and Calorimetry》2012,110(1):137-143
The aim of this research was to analyse composition, fatty acids distribution and oxidative stability of fats extracted from four samples of baby formulas. The fats were oxidized in a differential scanning calorimeter (DSC) under polythermal (dynamic) conditions and at normal pressure. The DSC experiments were carried out in an oxygen flow atmosphere using different, linearly programmed, heating rates in the range of 4?C12.5?°C/min. The extrapolated onset temperatures were determined using DSC exotherms and used for the assessment of the thermal oxidative stabilities of the samples. Activation energies (E a), pre-exponential factors (Z) and reaction rate constants (k) for oil oxidation under DSC conditions were calculated using the Ozawa?CFlynn?CWall method and the Arrhenius equation. The melting characteristics of the studied fats were obtained. The fats extracted from the agglomerated samples with higher onset temperatures were more stable than the fats extracted from the initial samples of baby formulas. 相似文献