全文获取类型
收费全文 | 8640篇 |
免费 | 185篇 |
国内免费 | 10篇 |
专业分类
化学 | 4926篇 |
晶体学 | 193篇 |
力学 | 185篇 |
数学 | 1362篇 |
物理学 | 2169篇 |
出版年
2022年 | 106篇 |
2021年 | 193篇 |
2020年 | 120篇 |
2019年 | 170篇 |
2018年 | 162篇 |
2017年 | 161篇 |
2016年 | 284篇 |
2015年 | 215篇 |
2014年 | 291篇 |
2013年 | 665篇 |
2012年 | 446篇 |
2011年 | 476篇 |
2010年 | 383篇 |
2009年 | 364篇 |
2008年 | 428篇 |
2007年 | 412篇 |
2006年 | 371篇 |
2005年 | 305篇 |
2004年 | 263篇 |
2003年 | 253篇 |
2002年 | 210篇 |
2001年 | 163篇 |
2000年 | 142篇 |
1999年 | 108篇 |
1998年 | 115篇 |
1997年 | 92篇 |
1996年 | 88篇 |
1995年 | 117篇 |
1994年 | 71篇 |
1993年 | 59篇 |
1992年 | 76篇 |
1991年 | 48篇 |
1990年 | 74篇 |
1989年 | 68篇 |
1988年 | 68篇 |
1987年 | 60篇 |
1986年 | 69篇 |
1985年 | 107篇 |
1984年 | 118篇 |
1983年 | 70篇 |
1982年 | 70篇 |
1981年 | 78篇 |
1980年 | 87篇 |
1979年 | 58篇 |
1978年 | 65篇 |
1977年 | 71篇 |
1976年 | 64篇 |
1975年 | 59篇 |
1974年 | 50篇 |
1973年 | 43篇 |
排序方式: 共有8835条查询结果,搜索用时 15 毫秒
951.
952.
Sylwia Studzińska Sandra Mounicou Joanna Szpunar Ryszard Łobiński Bogusław Buszewski 《Analytica chimica acta》2015
This text presents a novel method for the separation and detection of phosphorothioate oligonucleotides with the use of ion pair ultra high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry The research showed that hexafluoroisopropanol/triethylamine based mobile phases may be successfully used when liquid chromatography is coupled with such elemental detection. However, the concentration of both HFIP and TEA influences the final result. The lower concentration of HFIP, the lower the background in ICP-MS and the greater the sensitivity. The method applied for the analysis of serum samples was based on high resolution inductively coupled plasma mass spectrometry. Utilization of this method allows determination of fifty times lower quantity of phosphorothioate oligonucleotides than in the case of quadrupole mass analyzer. Monitoring of 31P may be used to quantify these compounds at the level of 80 μg L−1, while simultaneous determination of sulfur is very useful for qualitative analysis. Moreover, the results presented in this paper demonstrate the practical applicability of coupling LC with ICP-MS in determining phosphorothioate oligonucleotides and their metabolites in serum within 7 min with a very good sensitivity. The method was linear in the concentration range between 0.2 and 3 mg L−1. The limit of detection was in the range of 0.07 and 0.13 mg L−1. Accuracy varied with concentration, but was in the range of 3%. 相似文献
953.
Mind the correct basis set: A case study for predicting gas phase acidities of small compounds using calculations from first principles 下载免费PDF全文
Nina Tymińska Marta Włoch A. Timothy Royappa 《International journal of quantum chemistry》2015,115(1):42-49
Some of the most popular computational methods have been utilized to determine a dependency of the acidity trend of the first‐row hydrides on a choice of basis set. For about three decades, methyl anion ( ) was known as the strongest base but after Tian et al. were able to produce the gas phase lithium monoxide anion (LiO–) they discovered it was a stronger base than (Tian et al., Proc Natl Acad Soc USA 2008, 105, 7647). Furthermore, the authors confirmed their experimental results using high‐level ab initio methods, namely W1 and W2C composite methods, as well as complete active space‐averaged quadratic coupled cluster and Brueckner Doubles with triple excitation contribution (BD(T)) within the aug‐cc‐pVQZ basis set. These methods are highly demanding in terms of the computational effort as well as a level of expertise needed from the user to correctly conduct such calculations. We have shown that the proper acidity trend, that is, , can be obtained with less expensive, ”black‐box” type methods if only the basis set is properly chosen. Our results prove that the diffuse augmented basis sets are absolutely necessary for appropriate predictions of acidities. Our calculations show that the correct order of is achieved by augmenting relatively small cc‐pVXZ (X = D,T) basis sets. A similar effect is observed for the family of Pople's basis sets. Our estimate for with CCSD(T)/aug‐cc‐pVTZ was 423.8 kcal/mol, which agrees very well with the experimental value 425.7 ± 6.1 kcal/mol. An important finding is that the proper acidity trend may be reversed if the basis sets are not correctly selected. © 2014 Wiley Periodicals, Inc. 相似文献
954.
Agata Krakowska Witold Reczyński Włodzimierz Opoka Waldemar Turski 《International journal of environmental analytical chemistry》2015,95(9):855-866
Honey is a sweet product made by bees using nectar from flowers. Concentrations of Ca, K, Mg, Fe, Zn, Mn, Cu, Pb and Cd were determined in 13 honey samples from the selected regions around the world. Levels of Ca, Mg, Cu, Fe, Zn and Mn were measured using flame atomic absorption spectrometry (FAAS). Potassium concentration was determined via flame photometry. Concentrations of Cd and Pb were determined using the electrothermal technique (ETAAS). It was estimated that the examined samples of honey from Greece, Turkey, Spain, Poland, Mexico, Argentina and Italy were of good quality in terms of metal concentrations (compliant with the norms referring to food products – WHO, Fifty-third Report of the joint FAO/WHO Expert Committee on Food Additives; Technical Report Series 776, Geneva), although the analysed samples were not free of heavy metals. The concentrations of the elements in the honey samples ranged from 2.38 to 9.31 μg · g?1 for Zn, from 3.86 to 35.10 μg · g?1 for Fe, from 0.19 to 21.64 μg · g?1 for Mn, from 49.53 to 1006.90 μg · g?1 for Ca, from 388.25 to 4761.50 μg · g?1 for K and from 0.20 to 1.53 μg · g?1 for Cu and regarding heavy metals from 0.11 to 2.78 μg · g?1 for Pb and from 0.02 to 0.44 μg · g?1 for Cd. According to these results it was found that the concentrations of heavy metals in the honey samples (except for alfalfa honey and eucalyptus honey from Italy) were under the acceptable limits for foods set out by the FAO/WHO. It was confirmed that the application of chemometric tools supports the extraction of significant information from analytical data, even though the availability of samples is not fully sufficient (this problem is often encountered in environmental analyses). 相似文献
955.
Magdalena Jabłońska 《Chemical Papers》2015,69(9):1141-1155
Copper or iron supported on commercially available oxides, such as γ-Al2O3, TiO2 (anatase) and monoclinic tetragonal ZrO2 (mt-ZrO2) were tested as catalysts for selective catalytic oxidation of ammonia into nitrogen and water vapour (NH3-SCO) in the low temperature range. Different commercial oxides were used in this study to determine the influence of the specific surface area, acidic nature of the support and crystalline phases as well as of the type of species and aggregation state of transition metals on the catalytic performance in selective ammonia oxidation. Copper modified oxide supports were found to be more active and selective to nitrogen than catalysts impregnated with iron. Activities of both transition metal modified samples decreased in the following order: mt-ZrO2, TiO2 (anatase), γ-Al2O3. Quantitative total ammonia conversion was achieved with the Cu/ZrO2 catalytic system at 400°C. Characterisation techniques, e.g. H2-temperature programmed reduction, UV-VIS-diffuse reflectance spectroscopy, suggest that easily reducible copper oxide species are important in achieving high catalytic performances at low temperatures. 相似文献
956.
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
957.
Lanthanide Complexes with Multidentate Oxime Ligands as Single‐Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems 下载免费PDF全文
Dr. Małgorzata Hołyńska Dr. Rodolphe Clérac Mathieu Rouzières 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13321-13329
The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 ( 1 : [La2(pop)2(acac)4(CH3OH)], 2 : [Dy2(pop)(acac)5]) are synthesized from the 2‐hydroxyimino‐N‐[1‐(2‐pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3 , 4 , and 5 ( 3 : [Dy2(naphthsaoH)2(acac)4H(OH)]?0.85 CH3CN?1.58 H2O; 4 : [Tb2(naphthsaoH)2(acac)4H(OH)]?0.52 CH3CN?1.71 H2O; 5 : [La6(CO3)2(naphthsao)5 (naphthsaoH)0.5(acac)8(CO3)0.5(CH3OH)2.76H5.5(H2O)1.24]?2.39 CH3CN?0.12 H2O) contain 1‐(1‐hydroxynaphthalen‐2‐yl)‐ethanone oxime (naphthsaoH2). In 1 – 4 , dinuclear [Ln2] complexes crystallize, whereas hexanuclear LaIII complex 5 is formed after fixation of atmospheric carbon dioxide. DyIII‐based complexes 2 and 3 display single‐molecule‐magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy3+ ions. 相似文献
958.
Alina Sionkowska Sławomir Skrzyński Krzysztof Śmiechowski Agata Kołodziejczak 《先进技术聚合物》2017,28(1):4-9
This review reports recent advances in the versatile application of collagen. Collagen materials have attracted great attention because they exhibit properties required in cosmetic preparations, in the biomedical field, and in the tanning industry leading to leather production. Herein, the structure and application of collagen are discussed in general, and detailed examples are also drawn from scientific literature and practical work. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
959.
Synthesis of β-cyclodextrin-lysozyme conjugates and their physicochemical and biochemical properties
Tomasz Marek Goszczyński Maciej Gawłowski Beata Girek Konrad Kowalski Janusz Boratyński Tomasz Girek 《Journal of inclusion phenomena and macrocyclic chemistry》2017,87(3-4):341-348
Recently a great interest in the field of protein engineering and the design of innovative drug delivery systems employing specific ligands such as cyclodextrins is observed. The paper reports the solid state, thermal method for protein coupling with β-cyclodextrin and the physicochemical and biological properties of the obtained conjugates. The structure of the obtained conjugates was investigated via liquid chromatography-mass spectrometry, dynamic light scattering and circular dichroism analysis. The presented conjugates were biologically active and covalently bound β-cyclodextrin preserved the ability to form inclusion complexes with the model compound. This report demonstrates the great potential of cyclodextrin as a modifying unit that can be used to modulate the properties of therapeutic proteins, additionally giving such conjugates the possibility to transport many therapeutic substances in the form of inclusion complexes. In addition, the paper presents the potential of protein-cyclodextrin conjugates to construct innovative bioactive molecules for biological and medical applications. 相似文献
960.