全文获取类型
收费全文 | 12056篇 |
免费 | 781篇 |
国内免费 | 391篇 |
专业分类
化学 | 7512篇 |
晶体学 | 81篇 |
力学 | 491篇 |
综合类 | 40篇 |
数学 | 1989篇 |
物理学 | 3115篇 |
出版年
2024年 | 21篇 |
2023年 | 134篇 |
2022年 | 363篇 |
2021年 | 377篇 |
2020年 | 405篇 |
2019年 | 353篇 |
2018年 | 301篇 |
2017年 | 276篇 |
2016年 | 490篇 |
2015年 | 493篇 |
2014年 | 489篇 |
2013年 | 758篇 |
2012年 | 822篇 |
2011年 | 952篇 |
2010年 | 581篇 |
2009年 | 558篇 |
2008年 | 739篇 |
2007年 | 692篇 |
2006年 | 617篇 |
2005年 | 566篇 |
2004年 | 453篇 |
2003年 | 367篇 |
2002年 | 349篇 |
2001年 | 210篇 |
2000年 | 132篇 |
1999年 | 160篇 |
1998年 | 110篇 |
1997年 | 116篇 |
1996年 | 115篇 |
1995年 | 102篇 |
1994年 | 111篇 |
1993年 | 85篇 |
1992年 | 74篇 |
1991年 | 66篇 |
1990年 | 62篇 |
1989年 | 49篇 |
1988年 | 44篇 |
1987年 | 48篇 |
1986年 | 36篇 |
1985年 | 54篇 |
1984年 | 59篇 |
1983年 | 29篇 |
1982年 | 57篇 |
1981年 | 31篇 |
1980年 | 35篇 |
1979年 | 51篇 |
1978年 | 41篇 |
1977年 | 24篇 |
1976年 | 29篇 |
1974年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
111.
Two series of nano-sized N-containing MOx–ZnO (M: Fe, W) composite powders were synthesized by spray pyrolysis. The nitrogen content was controlled from 500 to 2100 ppm by changing the powder ingredients and spray pyrolysis temperature. Ultraviolet-visible (UV-Vis) spectra indicated that the N-containing MOx–ZnO powders absorbed not only ultraviolet light (λ<387 nm) like pure ZnO powder, but also part of visible light (λ<650 nm). Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these composite powders. The photocatalytic activity of the N-containing ZnO powder was pronouncedly enhanced by the WO3 addition under both UV and visible-light irradiation. However, that of the N-containing ZnO powder was suppressed by the Fe2O3 addition. A model of the semiconductor energy-band structure is proposed to explain the enhancement and suppression of photocatalytic activity. 相似文献
112.
X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), rotating disc electrode-electrochemical impedance spectroscopy (RDE-EIS) and synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) have been used to study the response mechanism of the mercury(II) chalcogenide ion-selective electrode (ISE) in saline media. XPS and SIMS have shown that the chalcogenide surface is poisoned by silver chloride, or a mixture of silver halides, on continuous exposure to synthetic and real seawater. Significantly, the in-situ SR-GIXRD study demonstrated that electrode fouling in synthetic seawater is linked to the formation of poorly crystalline or amorphous silver chloride, and that the low level of free mercury(II) in a calibration buffer (i.e., 10(-14) M) is able to undergo metathesis with silver(II) sulfide in the membrane generating mercury(II) sulfide. Significantly, the results of this detailed surface study have shown that silver chloride fouling of the electrode is ameliorated in real seawater comprising natural organic ligands, and this has been attributed to the peptization of silver chloride by the surfactant-like nature of seawater ligands at pH 8. RDE-EIS aging studies have revealed that the chalcogenide membrane experiences a sluggish charge transfer reaction in seawater, and contrary to a previous report for a static electrode, the seawater matrix does not passivate the RDE. The results of this XPS, SIMS, RDE-EIS and SR-GIXRD study have elucidated the response mechanism of the mercury(II) ISE in saline media. 相似文献
113.
Cozzolino R Di Giorgi S Fisichella S Garozzo D Lafiandra D Palermo A 《Rapid communications in mass spectrometry : RCM》2001,15(10):778-787
This study describes the verification of the cDNA-deduced amino acid sequences of high molecular weight glutenin subunits 1Dy10 and 1Bx7 in Cheyenne cultivar by direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis of their tryptic fragments omitting chromatographic pre-separation. These polypeptides have a conserved structure consisting of a long central repetitive domain that prevents the application of conventional sequencing procedures such as Edman degradation. The published sequence of subunit 1Dy10 contains 7 Lys and 13 Arg residues; thus the production of 21 tryptic peptides is expected. The cDNA-deduced sequence for 1Bx7 subunit includes 5 Lys and 15 Arg residues, but the presence of three Arg-Pro bonds, which are normally not cleaved by trypsin, predicts only 19 tryptic peptides. Three different matrices (DHB, SA and HCCA) in combination with the most compatible sample preparation procedures were used in order to obtain the maximum 1Dy10 and 1Bx7 sequence coverage. MALDI analysis of the 1Dy10 tryptic digest resulted in the identification of all 21 expected peptides. In the case of 1Bx7 MALDI analysis resulted in the identification of 17 of the 19 expected peptides, giving a sequence coverage of 99.3%. These results were sufficient to rule out glycosylation of the 1Dy10 and 1Bx7 proteins and to assess the absence of any other post-translational modification, to within the detection limits of the method. 相似文献
114.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
115.
Marco Vincenti Claudio Minero Stefania Lago Costanza Rovida 《Journal of separation science》1995,18(6):359-362
A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards. 相似文献
116.
二苯并-18-冠-6-甲醛聚合物柱色谱分离富集化学发光法测定痕量金 总被引:5,自引:0,他引:5
研究了用一种新的高分子冠醚聚合物(二苯并-18-冠-6-甲醛聚合物)作为色谱柱的固定相,分离富集痕量金,再用化学发光法进行测定;在盐酸介质中,高分子冠醚对金的吸附率可达100%,吸附的金可被硫脲完全解吸,吸附容量为19.40mg/g;化学发光法测定操作简便,效果令人满意;研究结果表明:把高分子冠醚聚合物作为分离富集手段与具有高灵敏度的化学发光法结合进行痕量分析是一种很有前途的方法。 相似文献
117.
Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending
on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient,
give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This
review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry
(FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS),
Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and
atom trapping mechanisms are presented.
Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970
Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br
Received December 20, 2001; accepted October 11, 2002 相似文献
118.
The adsorption of N-acetyl-L-cysteine from ethanol solution on gold has been studied by in situ attenuated total reflection infrared (ATR-IR) spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and a quartz crystal microbalance. After an initial fast adsorption, in situ ATR-IR revealed two considerably slower processes, besides further adsorption. The appearance of carboxylate bands and the partial disappearance of the carboxylic acid bands demonstrated that part of the molecules on the surface underwent deprotonation. In addition, the C=O stretching vibration of the carboxylic acid group shifted to lower and the amide II band to higher wavenumbers, indicating hydrogen-bonding interactions within the adsorbate layer. Based on the initial ATR-IR spectrum, which did not reveal deprotonation, the orientation of the molecule within the adsorbate layer was determined. For this, density functional theory was used to calculate the transition dipole moment vectors of the vibrational modes of N-acetyl-l-cysteine. The projections of the latter onto the z-axis of the fixed surface coordinate system were used to determine relative band intensities for different orientations of the molecule. The analysis revealed that the amide group is tilted with respect to and points away from the surface, whereas the carboxylic acid is in proximity to the surface, which is also supported by a shift of the C-O-H bending mode. This position of the acid group favors its deprotonation assisted by the gold surface and easily enables intermolecular interactions. Periodic acid stimuli revealed reversible protonation/deprotonation of part of the adsorbed molecules. However, only non-hydrogen-bonded carboxylic acid groups showed a response toward the acid stimuli. 相似文献
119.
A convenient route to new 3-quinolinonyl-pyrazoles and isoxazoles is described through cyclization of 3-[(E)-3-(dimethylamino)-2-propenoyl]-4-hydroxy-1-methyl-2(1H)-quinolinone. The phototoxicity as well as the cytotoxic activities of the title compounds are evaluated against leukemia- and adenocarcinoma-derived cell lines in comparison to the normal human keratinocytes. 相似文献
120.
Enza Di Gregorio Luciano Lattuada Alessandro Maiocchi Silvio Aime Giuseppe Ferrauto Eliana Gianolio 《Chemical science》2021,12(4):1368
The set-up of reversible binding interactions between the hydrophobic region of macrocyclic GBCAs (Gadolinium Based Contrast Agents) and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancements of this class of MRI contrast agents. The strong binding affinity allows attaining relaxation enhancements up to 50% at pyrene/GBCA ratios of 3 : 1. High resolution NMR spectra of the Yb-HPDO3A/pyrene system fully support the formation of a supramolecular adduct based on the set-up of hydrophobic interactions. The relaxation enhancement may be accounted for in terms of the increase of the molecular reorientation time (τR) and the number of second sphere water molecules. This effect is maintained in blood serum and in vivo, as shown by the enhancement of contrast in T1w-MR images obtained by simultaneous injection of GBCA and pyrene derivatives in mice.The set-up of reversible binding interactions between the hydrophobic region of macrocyclic gadolinium based contrast agents and SO3−/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancement of MRI contrast agents. 相似文献