全文获取类型
收费全文 | 232篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 175篇 |
力学 | 3篇 |
数学 | 34篇 |
物理学 | 35篇 |
出版年
2024年 | 1篇 |
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 13篇 |
2019年 | 9篇 |
2018年 | 7篇 |
2017年 | 8篇 |
2016年 | 9篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 18篇 |
2012年 | 17篇 |
2011年 | 15篇 |
2010年 | 12篇 |
2009年 | 12篇 |
2008年 | 11篇 |
2007年 | 21篇 |
2006年 | 6篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 3篇 |
2001年 | 1篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1994年 | 4篇 |
1993年 | 1篇 |
1990年 | 2篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有247条查询结果,搜索用时 31 毫秒
1.
Kinetics and concentration profile associated with the regulated radiodegradation of bilirubin in an organic solvent were
assessed. The pure unconjugated specimen was prepared in chloroform (40.0 μM). The depletion of bilirubin was almost linear
with dose, and complete degradation was accomplished with doses in excess of 100 Gy. The method was also evaluated for the
explicit production of the long-wavelength isomer of biliverdin, which was characterized spectrometrically by an absorbance
band in the region 600–650 nm. Results including differences in air, N2 and O2 purged samples are presented to identify the atmospheric medium for optimum production of biliverdin. The process was regulated
by controlling the dose. The general rate constant of the depletion process was estimated at a dose rate of 5.67·10−2Gy·s−1. The method is a convenient substitute for light illumination studies of bilirubin.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
2.
Alkali Blue 6B-attached poly(2-hydroxyethyl methacrylate) (poly(HEMA)) microporous films were investigated as chelate forming sorbents for heavy metal removal. Poly(HEMA) microporous films were prepared by UV-initiated photo-polymerization of HEMA in the presence of an initiator (azobisisobutyronitrile (AIBN)). Alkali Blue 6B was attached covalently. These films with a swelling ratio of 58%, and carrying 14.8 mmol Alkali Blue 6B m(-2) which were then used in the removal of Cd(II), Zn(II) and Pb(II) from aqueous media. Adsorption rates were very high, equilibrium was achieved in about 30 min. The maximum adsorption of heavy metal ions onto the Alkali Blue 6B-attached films were 41.4 mmol m(-2) for Cd(II), 52.4 mmol m(-2) for Zn(II), and 64.5 mmol m(-2) for Pb(II). When the heavy metal ions competed during the adsorption from a mixture the adsorption values for Cd(II), Zn(II) and Pb(II) were quite close. Heavy metal ions were desorbed by using 0.1 M HNO(3). A significant amount of the adsorbed heavy metal ions (up to 95%) could be desorbed in 30 min. Repeated adsorption/desorption cycles showed the feasibility of these novel dye-attached microporous films for heavy metal removal. 相似文献
3.
Poly(p-chloromethylstyrene-ethyleneglycoldimethacrylate) polymeric microbeads, poly(p-CMS-EGDMA), were synthesized and 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (S4HD) was attached chemically onto the polymeric microbeads. Characterization of all microbeads was done by Fourier transform-infrared spectrometry (FT-IR) and elemental analyzer. The amount of attached 1,5,9,13-tetrathiacyclohexadecane-3,11-diol to the polymer was found to be 2.23 mmol g−1 polymers. The ligand attached microbeads, poly(p-CMS-EGDMA-S4HD), were used to examine the adsorption capacity of Pb(II), Cd(II), Hg(II) and Cr(II) ions for recovery, pre-concentration and the matrix elimination by changing the pH and the initial metal ion concentrations and also adsorption kinetics of the studied metal ions was determined. Pre-concentration factors for the studied toxic metal ions were found to be more than 500-fold and recovery was between 92 and 106%. In the drinking, lake, tap and sea-water samples from water lands, ultra-trace toxic metal ion concentrations were determined easily by using ligand modified microbeads after pre-concentration because of the high pre-concentration factor and easily matrix elimination using ligand modified microbeads. Reference sea-water material was used for the validation of the method and it was found that recovery, pre-concentration and the matrix elimination were performed perfectly. For the desorption of the toxic metal ions, 3 M HCl containing 0.8 M thiourea was used and desorption ratio was obtained more than 96%. 相似文献
4.
Zuhair S. Salih Peter Stegmüller Wolfgang Pfleiderer 《Journal of heterocyclic chemistry》1988,25(5):1443-1447
Acylations of 1,3-dimethyl- ( 1 ) and 1,3,7-trimethylpyrrolo[2,3-d]pyrimidine-2,4-dione ( 2 ) with anhydrides in the presence of trifluoroacetic acid proceed well to give in good yields the corresponding 7-acyl derivatives 3–11 . The 6-trichloroacetyl derivatives 5 and 6 are sensitive towards nucleophiles, which displace the trichloromethyl group easily by formation of the corresponding 6-carboxylic acid derivatives 12–23. The newly synthesized compounds have been characterized by elemental analysis, uv and 1H nmr spectra and pKa, determinations. 相似文献
5.
A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:13,14-tribenzo-9,12-dioksa-cyclopentadeca-1,5-diene was synthesized by reaction of 2,6-diaminopyridine and 1,2-bis(2-carboxyaldehyde phenoxy)ethane. Then, its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes were synthesized by the template effect by the reaction of 2,6-diaminopyridine and 1,2-bis(2-carboxyaldehyde phenoxy)ethane and Cu(NO3)2 · 3H2O, Ni(NO3)2 · 6H2O, Pb(NO3)2, Co(NO3)2 · 6H2O, La(NO3)3 · 6H2O, respectively. The ligand and its metal complexes have been characterized by elemental analysis, IR, 1H and 13C NMR, UV-Vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements, mass spectra, and cyclic voltammetry. All complexes are diamagnetic and Cu(II) complex is binuclear. The Co(II) was oxidized to Co(III). The comparative electrochemical studies show that the nickel complex exhibited a quasi-reversible one-electron reduction process, while copper and cobalt complexes gave irreversible reduction processes in DMSO solution. 相似文献
6.
A. C. Altunisik S. Adanur A. F. Genc M. Gunaydin F. Y. Okur 《Experimental Mechanics》2017,57(2):245-259
Determining the structural behavior of masonry structures is a challenge due to their lack of homogeneity. The seismic behavior of masonry structures is especially complex. The aim of this study was to examine the structural behavior of Za?anos Bastion using both experimental and numerical methods. The Operational Modal Analysis technique, including the Enhanced Frequency Domain Decomposition Method, and the Stochastic Subspace Identification Method were used to illustrate experimentally the dynamic characteristic of the bastion. A finite element model was developed using ANSYS software in order that the dynamic characteristics of the bastion, including natural frequencies and mode shapes, could be calculated numerically. Seismic analysis was carried out using the 1999 Kocaeli earthquake ground motion record to determine the linear and nonlinear seismic behavior of the bastion. The Turkish Earthquake Code and its general technical specifications were used to evaluate the seismic results. The results show that the maximum and minimum principal stresses exerted on the masonry components exceeded the code requirements at some points, but in general the requirements for the stresses were satisfied. 相似文献
7.
K. Furkan Sokmen Erhan Pulat Nurettin Yamankaradeniz Salih Coskun 《Heat and Mass Transfer》2014,50(2):199-210
In this study, experimental and numerical analysis was performed to define thermal deformation inside the head lamp because of usage plastic materials and thermal loads. Buoyancy, radiation and conjugate effects were considered. Velocity and temperature distributions were obtained and possible hot points and condense regions can be determined. Nusselt number distribution on cylindrical bulb were computed and compared with literature. Relatively important heat transfer increase in natural convection was found. 相似文献
8.
Selma Bal Sedat Salih Bal Abdullah Erener Hatice Nur Halipci Seyhan Akar 《Chemical Papers》2014,68(3):352-361
Four water soluble azo dyes, 4-(isopropyl)-2-[(E)-(4-chlorophenyl)diazenyl]phenol (L 1), 4-(isopropyl)-2-[(E)-(2,4-dichlorophenyl)diazenyl]phenol (L2), 4-(sec-butyl)-2-[(E)-(4-chlorophenyl) diazenyl]phenol (L 3), 4-(sec-butyl)-2-[(E)-(2,4-dichlorophenyl)diazenyl]phenol (L 4), and their Cu(II) and Ni(II) complexes were synthesized and characterized using spectroscopic methods. Examination of their thermal stability revealed similar decomposition temperature of approximately 260–300°C and that they were more thermally stable than their metal complexes. Ni(II) complexes of ligands L2 and L4 were more stable than the other coordination compounds. Among the synthesized ligands, L2 and the complexes Cu(L3)2 and Ni(L4)2 showed both antimicrobial and antifungal activity. However, the other ligands and the complexes were poorly active against selected microorganisms. 相似文献
9.
Defect Chemistry of Singly and Doubly Doped Ceria: Correlation between Ion Transport and Energetics 下载免费PDF全文
Dr. Salih Buyukkilic Prof. Sangtae Kim Prof. Alexandra Navrotsky 《Angewandte Chemie (International ed. in English)》2014,53(36):9517-9521
Earlier studies have shown a strong correlation between the enthalpy of formation, ΔHf,ox, and the ionic conductivity, σi, near room temperature in doped ceria systems, which are promising solid electrolytes for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). The present work demonstrates that this correlation holds at the operating temperature of IT‐SOFCs, 600–700 °C. Solid solutions of Ce1?xNdxO2?0.5x, Ce1?xSmxO2?0.5x, and Ce1?xSm0.5xNd0.5xO2?0.5x are studied. The ΔHf,ox at 702 °C is determined by considering the excess heat content between 25 and 702 °C combined with the value of ΔHf,ox at 25 °C. Both σi and ΔHf,ox show maxima at x=0.15 and 0.20 for the singly and doubly doped ceria, respectively, suggesting that the number of mobile oxygen vacancies in these solid solutions reaches a maximum near those compositions. An increase in temperature results in a shift of the maximum in both ΔHf,ox and σi towards higher concentrations. This shift results from a gradual increase in dissociation of the defect associates. 相似文献
10.
M. Salih Ağırtaş Emrah Dede Selçuk Gümüş Abdurrahman Dündar Veysi Okumuş 《无机化学与普通化学杂志》2014,640(10):1953-1959
A novel phthalonitrile derivative bearing 2‐isopropyl‐6‐methylpyrimidin‐4‐yloxy substituents at peripheral positions was synthesized by a nucleophilic substitution reaction. Metallophthalocyanines were obtained from the reaction of the novel phthalonitrile with metal Zn, Cu, Co, and Ni salts. The characterization of the compounds was performed using elemental analysis as well as UV/Vis, FT‐IR, and 1H‐NMR spectroscopy. The aggregation behaviors of phthalocyanine complexes were also investigated. These metallophthalocyanines do not show any aggregation behavior between 10–4–10–6 M concentration range in THF. The antioxidant activities of the synthesized compounds were evaluated using three different tests: 2, 2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical scavenging, metal chelating activity, and reducing power assays. All the compounds exhibited various antioxidant activities. In addition, antimicrobial activity of the compounds was tested over four gram positive and two gram negative bacteria. Moreover, the ground‐state geometries of the complexes were optimized using density functional theory (DFT) methods at B3LYP/6‐31G(d, p) level in order to obtain information about the 3D arrangements and electronic structure. 相似文献