全文获取类型
收费全文 | 491篇 |
免费 | 24篇 |
国内免费 | 1篇 |
专业分类
化学 | 371篇 |
晶体学 | 9篇 |
力学 | 10篇 |
数学 | 75篇 |
物理学 | 51篇 |
出版年
2024年 | 2篇 |
2023年 | 5篇 |
2022年 | 29篇 |
2021年 | 22篇 |
2020年 | 26篇 |
2019年 | 32篇 |
2018年 | 19篇 |
2017年 | 18篇 |
2016年 | 34篇 |
2015年 | 18篇 |
2014年 | 21篇 |
2013年 | 50篇 |
2012年 | 43篇 |
2011年 | 28篇 |
2010年 | 28篇 |
2009年 | 16篇 |
2008年 | 12篇 |
2007年 | 27篇 |
2006年 | 14篇 |
2005年 | 11篇 |
2004年 | 15篇 |
2003年 | 6篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1975年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有516条查询结果,搜索用时 22 毫秒
31.
In this study, radiocesium sorption on ceramic clay was investigated as a function of particle size and initial 137Cs concentration using a batch method. Ceramic clay samples taken from the Sö?üt(?nisar) clay deposit were composed of kaolinite, dickite and quartz. The equilibrium time and the liquid–solid ratio were determined as 60 min and 250 mL g?1, respectively. The distribution coefficients (K d) for variable liquid–solid ratio and the percentage adsorption (P Ad) were calculated. The values of K d and P Ad ranged from 483 to 3165 mL g?1 and 34–93%, respectively. The K d and P Ad values increased with increasing particle size, but decreased with increasing initial concentration. The sorption data were interpreted in terms of a Langmuir isotherm. The results indicated that the Sö?üt(?nhisar) ceramic clay has good sorption capacity for cesium. 相似文献
32.
The large ring cyclodextrins (with more than 8 glucose units) existence was first described in the 1950s. Because of their hard purification and low yield, these molecules were little studied until recently. Since large ring cyclodextrins have unique structures compared to α-, β- and γ-cyclodextrin, they could offer new opportunities for specific host-guest complex and thus enlarge the area of cyclodextrin applications. This paper gives a literature survey regarding the synthesis, the purification and the applications of cyclodextrins containing more than eight glucose units. 相似文献
33.
Eker F Cao X Nafie L Schweitzer-Stenner R 《Journal of the American Chemical Society》2002,124(48):14330-14341
We have measured the band profile of amide I in the infrared, isotropic, and anisotropic Raman spectra of L-alanyl-D-alanyl-L-alanine, acetyl-L-alanyl-L-alanine, L-vanyl-L-vanyl-L-valine, L-seryl-L-seryl-L-serine, and L-lysyl-L-lysyl-L-lysine at acid, neutral, and alkaline pD. The respective intensity ratios of the two amide I bands depend on the excitonic coupling between the amide I modes of the peptide group. These intensity ratios were obtained from a self-consistent spectral decomposition and then were used to determine the dihedral angles between the two peptide groups by means of a recently developed algorithm (Schweitzer-Stenner, R. Biophys. J. 2002, 83, 523-532). The validity of the obtained structures were checked by measuring and analyzing the vibrational circular dichroism of the two amide I bands. Thus, we found two solutions for all protonation states of trialanine. Assuming a single conformer, one obtains a very extended beta-helix-like structure. Alternatively, the data can be explained by the coexistence of a 3(1)(PII) and a beta-sheet-like structure. Acetyl-L-alanyl-L-alanine exhibits a structure which is very similar to that obtained for trialanine. The tripeptide with the central D-alanine adopts an extended structure with a negative psi and a positive phi angle. Trivaline and triserine adopt single beta(2)-like structures such as that identified in the energy landscape of the alanine dipeptide. Trilysine appears different from the other investigated homopeptides in that it adopts a left-handed helix which at acid pD is in part stabilized by hydrogen bonding between the protonated carboxylate (donor) and the N-terminal peptide carbonyl. Our result provides compelling evidence for the capability of short peptides to adopt stable structures in an aqueous solution, which at least to some extent reflect the intrinsic structural propensity of the respective amino acids in proteins. Furthermore, this paper convincingly demonstrates that the combination of different vibrational spectroscopies provides a powerful tool for the determination of the secondary structure of peptides in solution. 相似文献
34.
Fayez H.?OsmanEmail author Fatma A.?El-Samahy I. S.?Ahmed Farag 《Monatshefte für Chemie / Chemical Monthly》2004,135(7):823-831
Summary. The reaction of (E)-(2-oxo-1,2-dihydroindol-3-ylidene)acetic acid esters with dry acetone at 70°C in presence of aluminum oxide as a catalyst led to the formation of an addition product as a mixture of two isomers. When the same reaction was carried out in presence of morpholine as a base, the unexpected spiro-product was obtained beside the two isomers. Methylation of the latter with methyl iodide in acetone in presence of anhydrous potassium carbonate yielded the corresponding methylated products, whereas methylation of the starting material by the same procedure gave an N-methylated product and the unexpected dispiro-compound. The reaction mechanisms are considered and the structural assignments of the new compounds are based on the chemical and spectroscopic evidences. The structure of the dispiro-product was derived by X-ray analysis. 相似文献
35.
36.
In this work, we consider a nonlinear system of viscoelastic equations of Kirchhoff type with degenerate damping and source terms in a bounded domain. Under suitable assumptions on the initial data, the relaxation functions gi(i = 1,2) and degenerate damping terms, we obtain global existence of solutions. Then, we prove the general decay result. Finally, we prove the finite time blow‐up result of solutions with negative initial energy. This work generalizes and improves earlier results in the literature. 相似文献
37.
Utility of 4‐Benzylidene‐2‐phenyl‐5(4H)‐oxazolone in Synthesis of Triazine,Oxadiazole and Imidazole Derivatives of Anticipated Biological Activity 下载免费PDF全文
Ahmed S. A. Youssef Fatma A. El‐Mariah Fatma T. Abd‐Elmottaleb Heba E. Hashem 《Journal of heterocyclic chemistry》2015,52(5):1467-1473
Treatment of oxazolone 1 with hydrazine hydrate at room temperature gave the (Z)‐configurated isomer hydrazide (Z)‐ 3 (high yield). However, refluxing 1 with hydrazine hydrate yielded the (E)‐configurated isomer hydrazide (E)‐ 2 (low yield).The hydrazide derivative (Z)‐ 3 has been utilized as synthon for the synthesis of 1,2,4‐triazinone, imidazolone, and oxadiazole derivatives through appropriate routes. The thiosemicarbazide and semicarbazide derivatives are synthesized by different routes. The structures of the new compounds were established on the basis of IR, 1H‐NMR, mass spectral data, and elemental analysis. 相似文献
38.
Kamal A. Idriss Magda S. Saleh Mohamed M. Seleim Fatma S. Hassan Sherif K. Idriss 《Monatshefte für Chemie / Chemical Monthly》1990,121(8-9):625-634
Summary A simple, rapid, selective, and sensitive method for the spectrophotometric determination of palladium is developed based on the reaction of Pd(II) with 1-amino-4-hydroxyanthraquinone (AMHA). The reaction is carried out atpH 3.8 in 50% (v/v) ethanol-water medium. The molar absorptivity of the complexed ligand is 1.1 · 104 l mol–1 cm–1 at 620 nm. Calibration plots are linear up to 17 µg Pd cm–3. The optimum concentration range (Ringbom plot) is between 3–14.5 µg cm–3. The spectral study of the reaction in solutions containing equimolar concentrations or an excess of one component, in thepH range 0.3–6.5, indicate the possible complex transitions that occur in solution. Complete graphical and logarithmic analysis of the absorbance-pH graphs was performed to demonstrate and characterize the complexation equilibria in solution. Under the optimum conditions, palladium can be determined as the noncharged complex Pd(AMHA)2 in the presence of a large number of foreign ions. Interferences caused by zirconium(IV) could be masked with fluoride ions.
Eine neue spektrophotometrische Methode für die Bestimmung von Palladium in Spuren
Zusammenfassung Eine einfache, schnelle und empfindliche Methode für die spektrophotometrische Bestimmung von Palladium wurde auf der Basis der Reaktion von Pd(II) mit 1-Amino-4-hydroxyanthrachinon (AMHA) entwickelt. Die Reaktion wird in 50% (v/v) Ethanol/Wasser beipH 3.8 ausgeführt. Die molare Absorption des komplexierten Liganden beträgt 1.1 · 104 l mol–1 cm–1 bei 620 nm. Kalibrierungskurven verlaufen bis zu 17 µg Pd cm–3 linear. Der optimale Konzentrationsbereich (Ringbom-Plot) liegt zwischen 3 und 14.5 µg cm–3. Spektroskopische Untersuchungen der Reaktion in Lösungen, entweder mit equimolaren Konzentrationen oder mit einem Überschuß an einer Komponente impH-Bereich 0.3–6.5, lassen Rückschlüsse auf mögliche Komplex-Übergänge in Lösung zu. Es wurde eine vollständige graphische, logarithmische Analyse der Absorptions-pH-Graphen durchgeführt, um die Komplexgleichgewichte in Lösung aufzuklären und zu charakterisieren. Unter den Optimalbedingungen kann Palladium als nichtgeladener Komplex Pd(AMHA)2 in Gegenwart einer großen Anzahl an Fremd-Ionen bestimmt werden. Schwierigkeiten mit Zirkonium(IV) konnte durch Maskierung mit Fluorid-Ionen umgangen werden.相似文献
39.
The effect of addition of sodium anthranilate to 5 mM micellar solutions of gemini surfactant 1,4-bis(N-hexadecyl-N,N-dimethylammonium)butane dibromide is investigated by 1H NMR. The solubilization site of anthranilate anion near the micellar surface is inferred. In the micelles, the An− ions intercalate among the surfactant headgroups producing morphological changes. 相似文献
40.
A quartz crystal microbalance DNA biosensor based on plasma prepared polythiophene /titanium dioxide (PT/TiO2) nanocomposite was developed for the detection of genetically modified organisms (GMOs). DNA hybridization was studied by quartz crystal microbalance (QCM) and cyclic voltammetry (CV) measurements. Single stranded DNA probes were immobilized on the PT/TiO2 coated quartz crystal electrode and the hybridization between the immobilized probe and the target complementary sequence in solution was monitored. The developed QCM-DNA biosensor represented promising results for a real-time, label-free, direct detection of DNA samples for the screening of genetically modified organisms. 相似文献