全文获取类型
收费全文 | 1797篇 |
免费 | 68篇 |
国内免费 | 11篇 |
专业分类
化学 | 1413篇 |
晶体学 | 22篇 |
力学 | 60篇 |
数学 | 112篇 |
物理学 | 269篇 |
出版年
2023年 | 9篇 |
2022年 | 20篇 |
2021年 | 51篇 |
2020年 | 40篇 |
2019年 | 48篇 |
2018年 | 46篇 |
2017年 | 45篇 |
2016年 | 83篇 |
2015年 | 64篇 |
2014年 | 115篇 |
2013年 | 157篇 |
2012年 | 138篇 |
2011年 | 153篇 |
2010年 | 83篇 |
2009年 | 63篇 |
2008年 | 109篇 |
2007年 | 112篇 |
2006年 | 89篇 |
2005年 | 89篇 |
2004年 | 53篇 |
2003年 | 47篇 |
2002年 | 44篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 19篇 |
1997年 | 12篇 |
1996年 | 13篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 12篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1969年 | 2篇 |
1964年 | 5篇 |
排序方式: 共有1876条查询结果,搜索用时 62 毫秒
51.
Eight differently substituted title dye compounds have been investigated regarding intersystem crossing, triplet state, fluorescence and singlet excited state pKa properties. In general, non-halogenated oxazines and thiazines as well as a mono bromooxazine show very low triplet quantum yields, phi tau (less than 0.03) and relatively long triplet lifetimes (approximately 40 microseconds) in acidic methanol. The phi tau data correlate well with known singlet oxygen yields. In basic methanol no triplet transient is observed but a significant yield of a ground state transient protonated (base dye) form is produced with a short lifetime, approximately 400 ns. Fluorescence can be seen simultaneously from both the excited base and the protonated base dye forms in basic methanol. For iodinated oxazine or thiazines, the triplet yield increases and can be as high as 0.5 (diiodo case) in acidic methanol. The triplet lifetimes are further shortened to approximately 10 microseconds compared to the non-iodinated derivatives above. The triplet yields of the iodo compounds are higher or equal to known singlet oxygen yields. In basic methanol triplet yields up to 0.2 can be seen, the triplet lifetime are shortened still further to 1 microsecond but no observable protonated form is produced (in distinction to the non-iodinated cases). Consideration is given to the correlation of triplet and singlet oxygen yields, ground and excited pKa properties, spin-orbit coupling and internal conversion properties, solvent effects, and phototherapeutic activity of these dyes. 相似文献
52.
K. Suresh G. V. Mahesh K. C. Patil 《Journal of Thermal Analysis and Calorimetry》1989,35(4):1137-1143
Fine particle cobalt doped-Fe2O3 and Mn-Zn ferrites have been prepared by the thermal decomposition of N2H5Co
x
Fe1–x
(N2H3COO)3.H2O wherex=1–10 atom% and (N2H5)3MnxZn1–x
Fe2(N2H3COO)9· 3H2O wherex=0.2–0.8, respectively. Formation of these oxide materials has been confirmed by thermogravimetry and X-ray powder diffraction patterns. The fine particle nature of these oxide materials is evident from particle size analysis and surface area measurements.
Zusammenfassung Mit fein verteiltem Kobalt versetztes-Fe2O3 sowie Mn-Zn Ferrite wurden durch thermische Zersetzung von N2H5Co x Fe1–x (N2H3COO)3·H2O mit jc=1–10 Atomprozent bzw. (N2H5)3Mn x Zn1–x Fe2(N2H3COO)9·3H2O mitx=0,2–0,8 hergestellt. Die Bildung dieser Oxidstoffe wurde durch Thermogravimetrie und Pulverdiffraktionsmethoden bekräftigt. Die Feinkornstruktur dieser Oxidstoffe wird durch Korngrößenverteilungs- und Oberflächenmessungen augenscheinlich.
N2H5Co x Fe1–x (N2H3COO)3·H2O, x-1–10 %, (N2H5)3Mn x Zn1–x Fe2(N2H3COO)9 · 3H2O, x=0,2–0,8, , , -Fe2O3 Mn-Zn . . .相似文献
53.
Isobaric vapor–liquid equilibrium data at 95.96 kPa for the three binary systems of 2,2,4-trimethylpentane with methyl tert-butyl ether, di-isopropyl ether and dimethoxymethane are determined. A Swietoslawski type ebulliometer is used for the measurements. The experimental T–x data are used to estimate Wilson parameters and the parameters, in turn, are used to calculate vapor phase compositions and activity coefficients. All the systems studied here do not exhibit azeotropes and behave like non-ideal solutions. 相似文献
54.
By the use of time domain reflectometry method, dielectric measurements were carried out on dimethylformamide‐2‐nitrotoluene solvent mixtures in the frequency range 10 MHz‐20 GHz, at various temperatures from 15 °C to 45 °C. These solvent mixtures as well as pure solvents display a Debye type dispersion. Their frequency dependent dielectric properties can be summarized by the three parameters in the Debye equation: a static permittivity, permittivity at high frequency and a dielectric relaxation time constant. The free energy of activation for dipolar relaxation process and the Kirkwood correlation factor were determined using these fitting parameters for these solvent mixtures at various concentrations and temperatures. By using these dielectric parameters, the excess permittivity and excess inverse relaxation time is obtained. The excess permittivity is found to be positive for all concentrations and temperatures whereas the excess inverse relaxation time is negative. 相似文献
55.
Vasu Govardhana Reddy P Suresh Reddy C Naga Raju C 《Chemical & pharmaceutical bulletin》2003,51(7):860-863
N-(substituted)-N'-(2,3-dihydro-5-benzoyl-2-oxido-1H-1,3,2-benzodiazaphosphol-2-yl) ureas were synthesized by reacting 3,4-diaminobenzophenone (4) with different chlorides of carbamidophosphoric acids (3) in the presence of triethylamine at 40-45 degrees C. Their 1H-, 13C- and 31P-NMR spectral data are discussed. The title compounds were screened for antifungal and antibacterial activity against the fungi Aspergillus niger and Fusarium solani and bacteria Escherichia coli and Staphylococcus aureus. These compounds showed higher antibacterial activity when compared with antifungal activity. 相似文献
56.
Coupling of Fmoc-amino acid chlorides mediated by activated commercial zinc dust for the synthesis of peptides is described. The reaction is carried out in an organic medium. The necessity of using an inorganic base like NaHCO3/Na2CO3 or an organic base like DIEA/NMM/TEA/pyridine is circumvented. The coupling is reasonably fast, clean, racemization free and high yielding. 相似文献
57.
Kanchi Suvardhan Kailasa Suresh Kumar Dasari Rekha Pantrangam Subrahmanyam Kapuvedi Kiran Bellum Jayaraj Surasura Ramanaiah Kandhukuri Janardhanam Pattium Chiranjeevi 《Mikrochimica acta》2007,157(3-4):237-244
Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate
(2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed
with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished
by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully
applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL
sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL−1. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL−1), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium
in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test. 相似文献
58.
Awale S Tezuka Y Banskota AH Adnyana IK Kadota S 《Chemical & pharmaceutical bulletin》2003,51(3):268-275
From the methanolic extract of Indonesian Orthosiphon stamineus, nine new highly-oxygenated isopimarane-type diterpenes [7-O-deacetylorthosiphol B (1), 6-hydroxyorthosiphol B (2), 3-O-deacetylorthosiphol I (3), 2-O-deacetylorthosiphol J (4), siphonols A-E (5-9)] have been isolated together with nine known diterpenes [orthosiphols H (10), K (11), M (12) and N (13); staminols A (14) and B (15); neoorthosiphols A (16) and B (17); norstaminol A (18)]. Their structures were determined based on the spectroscopic data. The isolated diterpenes inhibited nitric oxide (NO) production in lipopolysaccharide (LPS)-activated macrophage-like J774.1 cells. Compounds 4-7, 9, 10, 14, and 17 showed inhibitory activities more potent (IC(50), 10.8-25.5 microM) than a positive control N(G)-monomethyl-L-arginine (L-NMMA; IC(50), 26.0 microM). 相似文献
59.
Poly(vinyl chloride) (PVC)-based membrane of pentathia-15-crown-5 exhibits good potentiometric response for Hg2+ over a wide concentration range (2.51 × 10−5 to 1.00 × 10−1 mol dm−3) with a slope of 32.1 mV per decade of Hg2+ concentration. The response time of the sensor is as fast as 20 s. The electrode has been used for a period of six weeks and exhibits fairly good discriminating ability towards Hg2+ in comparison to alkali, alkaline and some heavy metal ions. The electrode can be used in the pH range from 2.7 to 5.0. 相似文献
60.
Amphiphilic and hydrophilic oligomers were synthesized and coated on fused silica capillaries using a sol-gel technique. Sol-gel-coated capillaries were evaluated for the solid-phase microextraction and preconcentration of a wide variety of non-polar and polar analytes. Both types of coatings were stable under high temperature (up to 280 degrees C). The extraction efficiency of the sol-gel coatings was evaluated for the extraction of both non-polar and polar analytes, including organochlorine pesticides, triazine herbicides, estrogens and alkylphenols (APs) and bisphenol-A (BPA). Compared with commercially available solid-phase microextraction (SPME) adsorbents such as poly(dimethylsiloxane)divenylbenzene and polyacrylate, the new materials showed comparable selectivity and sensitivity towards both non-polar and polar analytes. The new coatings gave good linearity and detection limits. For example with triazines, a detection limit of <0.005 microl l(-1), precision from 5.0 to 11.0% (n = 6) and linearity of the calibration plots (0.5 to 50 microl l(-1)) were obtained. The sol-gel coated SPME capillaries were used for the determination of triazine herbicides in reservoir water samples collected in Singapore. 相似文献