全文获取类型
收费全文 | 2780篇 |
免费 | 89篇 |
国内免费 | 9篇 |
专业分类
化学 | 2502篇 |
晶体学 | 6篇 |
力学 | 17篇 |
数学 | 212篇 |
物理学 | 141篇 |
出版年
2023年 | 14篇 |
2022年 | 57篇 |
2021年 | 80篇 |
2020年 | 37篇 |
2019年 | 48篇 |
2018年 | 30篇 |
2017年 | 41篇 |
2016年 | 69篇 |
2015年 | 93篇 |
2014年 | 84篇 |
2013年 | 165篇 |
2012年 | 203篇 |
2011年 | 212篇 |
2010年 | 106篇 |
2009年 | 132篇 |
2008年 | 170篇 |
2007年 | 180篇 |
2006年 | 207篇 |
2005年 | 205篇 |
2004年 | 150篇 |
2003年 | 132篇 |
2002年 | 122篇 |
2001年 | 26篇 |
2000年 | 24篇 |
1999年 | 17篇 |
1998年 | 20篇 |
1997年 | 30篇 |
1996年 | 22篇 |
1995年 | 20篇 |
1994年 | 11篇 |
1993年 | 12篇 |
1992年 | 16篇 |
1991年 | 15篇 |
1990年 | 15篇 |
1989年 | 10篇 |
1988年 | 3篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 10篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1970年 | 2篇 |
1927年 | 2篇 |
排序方式: 共有2878条查询结果,搜索用时 15 毫秒
121.
Cristina Bucur Romana Cerc Korošec Mihaela Badea Larisa Calu Mariana Carmen Chifiriuc Nicoleta Grecu Nicolae Stanică Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1287-1295
Novel complexes of type M2LCl4·nH2O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV–vis, 1H NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells. 相似文献
122.
Maria Carmen Florian Eric Condamine loïc Toupet Yvan Ramondenc Gérard Plé 《Supramolecular chemistry》2013,25(6):383-392
The synthesis and the structure of new macrocycles containing semiflexible dispiro-1,3-dioxane units is reported. The structural analysis of the compounds is performed by high field NMR spectra, mass spectrometry investigations (MALDI, ESI-MS) and the solid state molecular structure obtained for two compounds by single crystal X-ray diffractometry. The dynamics of the macrocycles promoted by the flipping of the middle cyclohexane ring of the dispirane units is investigated using low temperature NMR experiments. New macrocycles containing dispiro-1,3-dioxane units were investigated by NMR, X-ray diffractometry and mass spectrometry 相似文献
123.
Carmen Palermo Marilena Muscarella Donatella Nardiello Marco Iammarino Diego Centonze 《Analytical and bioanalytical chemistry》2013,405(2-3):1015-1023
In the present work a sensitive and accurate method by ion chromatography and conductimetric detection has been developed for the determination of biogenic amines in food samples at microgram per kilogram levels. The optimized extraction procedure of trimethylamine, triethylamine, putrescine, cadaverine, histamine, agmatine, spermidine, and spermine from real samples, as well as the separation conditions based on a multilinear gradient elution with methanesulfonic acid and the use of a weak ionic exchange column, have provided excellent results in terms of resolution and separation efficiency. Extended calibration curves (up to 200 mg/kg, r?>?0.9995) were obtained for all the analyzed compounds. The method gave detection limits in the range 23–65 μg/kg and quantification limits in spiked blank real samples in the range 65–198 μg/kg. Recovery values ranged from 82 to 103 %, and for all amines, a good repeatability was obtained with precision levels in the range 0.03–0.32 % (n?=?4). The feasibility and potential of the method were tested by the analysis of real samples, such as tinned tuna fish, anchovies, cheese, wine, olives, and salami. Figure
IEC‐CD multiresidual method for accurate determinations of biogenic amines in foodstuffs 相似文献
124.
Natalia Ríos Cecilia Chavarría Carmen Gil Williams Porcal 《Journal of heterocyclic chemistry》2013,50(3):720-726
An efficient and rapid microwave‐assisted solid‐phase method for the synthesis of 5‐methyl‐1,2‐disubstituted benzimidazoles derivatives has been developed. The phosphonium linker, obtained by reaction between polymer‐supported triphenylphosphine and 4‐fluoro‐3‐nitrobenzyl iodide, underwent aromatic substitution with primary amines, followed by one‐pot reaction with aldehydes in the presence of SnCl2·2H2O, yielded the benzimidazole system under microwave irradiation. The final products were released from the resin with NaOH under microwave irradiation and were obtained in high purity and good overall yield. 相似文献
125.
Conjugated addition of alcohols to 9-hydroxy-and 9-methoxy-1, 4-anthraquinone, in the presence of a strong acid and an oxidant, affords the 2-alkoxy- and 3-alkoxy-substituted regioisomer, respectively. 相似文献
126.
M. Carmen Pérez Morales Dr. Julieta V. Catalán Dr. Victoriano Domingo Prof. Martín Jaraíz Dr. M. Mar Herrador Dr. José F. Quílez del Moral Prof. José‐Luis López‐Pérez Prof. Alejandro F. Barrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6598-6612
Treatment of germacrone ( 1 ) with different electrophiles, and of its epoxy derivatives germacrone‐4,5‐epoxide ( 2 ), germacrone‐1,10‐epoxide ( 3 ) and isogermacrone‐4,5‐epoxide ( 4 ) with Brönsted/Lewis acids and TiIII, gives rise to a great structural diversity. Thus, by using a maximum of two steps, the production of more than 40 compounds corresponding to 14 skeletons is described. Computational calculations rationalizing the structural divergence produced are also described. Finally, since some of the compounds generated are bioactive natural sesquiterpenes, the mechanisms of formation of these substances will provide new insights in their biosynthesis. 相似文献
127.
Alicia Monleón Prof. Dr. Gonzalo Blay Prof. Dr. Luis R. Domingo Prof. Dr. M. Carmen Muñoz Prof. Dr. José R. Pedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14852-14860
A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I2, Br2 and Cl2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed. 相似文献
128.
Carmen Ibáñez-Palomino J. Fermín López-Sánchez 《International journal of environmental analytical chemistry》2013,93(7):909-921
A systematic study of Hg2+ and CH3Hg+ (MeHg+) speciation using hyphenated techniques, was performed for high-performance liquid chromatography coupled to on-line UV irradiation and cold-vapour atomic fluorescence spectroscopy (HPLC-UV-CV-AFS). First, a comparative study of the behaviour of three mobile phase compositions (using tetrabutylammonium bromide (TBAB), L-cysteine and ammonium pyrrolidinedithiocarbamate (APDC)) is presented. The separation and detection system was optimised by considering factors that modify fluorescence signal and the separation such as, the addition of different percentages of an organic modifier (methanol (MeOH) and acetonitrile (ACN)) to the mobile phase, the type of reducing agent used (SnCl2 and NaBH4) and the potential memory effects of the material of which the injection system is made (stainless steel, PEEK). The mobile phase selected for its sensitivity was a mixture 80?:?20 MeOH?:?0.0015?mol?l–1 APDC and 0.01?mol?l–1 NH4CH3COO (pH 5.5). The detection and quantification limits were close to 1.5 and 5?µg?l?1 for both species (as Hg), respectively. Recoveries obtained using fortified water samples of distinct origin (soft mineral, tap, river, seawater, and wastewater), ranged from 90 to 115% for concentrations about 2 and 20 times over quantification limits. Good repeatability was obtained (about 5%) independently of the concentrations, with reproducibility values about 20% at low concentrations and 5–10% at higher concentrations. Our proposed method proved to be straightforward for use by environmental laboratories for routine Hg2+ and MeHg+ determinations in polluted water samples. 相似文献
129.
130.
Isabel Pizarro Ma Milagros Gomez Carmen Cámara Ma Antonia Palacios 《International journal of environmental analytical chemistry》2013,93(10):879-890
Gradient ion chromatographic separation coupled with ICP-MS was used to resolve and determine the most common arsenic species in environmental and biological samples of carrots, trout, soil, sediment and river water from Region II of Chile. The carrot and trout samples showed a concentration of 49 and 168 µg g?1, respectively, of total As. Both concentrations are high considering the basal level. In the carrots, percentage of 45 and 31% of total As were found for As(III) and As(V) species, respectively. In the trout, the higher concentration related to AsB at 39% of the total As. As(III) and DMA were also present in relatively high concentrations. The River Loa and the soil in which the carrots are growing also present very high As(V) concentrations of 100 and 17 µg g?1, respectively. The ratio between the concentration for the same As species found in the living organisms (carrots and trout) and the environment in which they grow (soil and water) can provide important information about the possible absorption or biotransformation of As species in living beings. As(III) and DMA are the species in which the greatest accumulation occurs with respect to the medium in which they are present, and biotransformation also appears to take place. 相似文献