全文获取类型
收费全文 | 365篇 |
免费 | 16篇 |
国内免费 | 3篇 |
专业分类
化学 | 281篇 |
晶体学 | 2篇 |
力学 | 8篇 |
数学 | 30篇 |
物理学 | 63篇 |
出版年
2023年 | 6篇 |
2022年 | 29篇 |
2021年 | 26篇 |
2020年 | 18篇 |
2019年 | 17篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 19篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 29篇 |
2012年 | 16篇 |
2011年 | 16篇 |
2010年 | 15篇 |
2009年 | 7篇 |
2008年 | 17篇 |
2007年 | 16篇 |
2006年 | 9篇 |
2005年 | 9篇 |
2004年 | 16篇 |
2003年 | 14篇 |
2002年 | 18篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1980年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1932年 | 1篇 |
排序方式: 共有384条查询结果,搜索用时 0 毫秒
1.
2.
The interfering effects of various foreign ions on the determination of arsenic were studied by hydride generation inductively coupled plasma atomic emission spectrometry (HG-ICP-AES). There were serious inhibiting interferences by Cu, Pb, Co, Au, Pd and Ni. However, by using cyanide as a complexing agent these interferences could be completely eliminated over a wide range of interferent concentration. The optimum chemical parameters for continuous arsine generation were studied. A major advantage of this technique is that it only needs low acid concentrations and produces less hazardous waste. Sensivity, selectivity and accuracy of the determination of arsenic by HG-ICP-AES were investigated. The detection limit (in 1 mol/l HCl medium) for arsenic(III) was 0.82 ng/ml. The relative standard deviation for ten determinations of a solution containing 50 ng/ml arsenic was 1.3%. 相似文献
3.
The solvation shell structure and dynamics of a single Cu2+ ion in a periodic box with 32 water molecules under ambient conditions has been investigated using Car-Parrinello molecular dynamics simulations in a time-window of 18 ps. Five-fold coordination with four equidistant equatorial water molecules at 2.00 A and one axial water molecule at 2.45 A from the Cu2+ ion is found. A "hole" without water molecules is found on the opposite side of the axial water. The ion-water bonding character for the equatorial water molecules is different from that of the axial water molecules, as shown by a localized orbital analysis of the electronic structure. Moreover, the calculated OD stretching vibrational band for the equatorial water molecules lies ca. 175 cm-1 below the axial-water band, in good agreement with experimental data. The equatorial-water band lies below, and the axial-water band above, the pure liquid D2O band, also in agreement with experimental data. 相似文献
4.
Rabab M. Amer Amira Kamel Eltokhy Rasha Osama Elesawy Amany Nagy Barakat Eman Basha Omnia Safwat Eldeeb Alshimaa Aboalsoud Nancy Mohamed Elgharabawy Radwa Ismail 《Molecules (Basel, Switzerland)》2022,27(12)
Introduction. Vigabatrin (VGB) is an antiepileptic drug that acts to irreversibly inhibit the γ-aminobutyric acid (GABA) transaminase enzyme, elevating GABA levels. Broad studies have established that long-term treatment and/or high doses of VGB lead to variable visual defects. However, little attention has been paid to its other side effects, especially those demonstrating cerebellar involvement. Sodium glucose-linked co-transporter 2 (SGLT2) inhibitors are antidiabetic agents with protective effects far greater than expected based on their anti-hyperglycemic effect. Method. Our study herein was designed to investigate the possible ameliorative effect of empagliflozin, the SGLT2 inhibitors, in VGB-induced cerebellar toxicity. A total of 40 male Wistar rats were allocated equally into 4 groups: Group I: control group; Group II: VGB group; Group III empagliflozin treated VGB group; and Group IV: empagliflozin treated group. All groups were subjected to the detection of cerebellar messenger RNA gene expression of silent mating type information regulation 2 homolog 1 (SIRT1) and Nucleoporin p62 (P62). Mammalian target of rapamycin (mTOR), adenosine monophosphate-activated protein kinase (AMPK), and beclin1 levels were assessed by the ELISA technique while malondialdehyde (MDA) level and superoxide dismutase (SOD) activity were detected spectrophotometrically. Immuno-histochemical studies, focusing on glial fibrillary acidic protein (GFAP) and S100 were performed, and the optical color density and the mean area percentage of GFAP positive astrocytes and the number of S 100 positive cells were also counted. Results. Following empagliflozin treatment, we documented significant upregulation of both SIRT1 and P62 mRNA gene expression. Additionally, AMPK, Beclin1 levels, and SOD activity were significantly improved, while both mTOR and MDA levels were significantly reduced. Conclusions. We concluded for the first time that empagliflozin efficiently ameliorated the VGB-induced disrupted mTOR/AMPK/SIRT-1 signaling axis with subsequent improvement of the autophagy machinery and mitigation of the oxidative and inflammatory cellular environment, paving the way for an innovative therapeutic potential in managing VGB-induced neurotoxicity. 相似文献
5.
A convenient and efficient reductive amination for the preparation of chiral β-amino amides is developed utilizing microwave heating. A variety of chiral β-keto amides react with ammonium acetate and sodium cyanoborohydride to afford the desired functionalized amines in good yields. This improved procedure takes advantage of microwave heating to significantly accelerate the reaction and offers a convenient and effective method to access some interesting molecules containing primary amine functionalities. 相似文献
6.
Daniel Riebe Robert Laudien Christian Brendler Toralf Beitz Hans-Gerd Löhmannsröben 《Analytical and bioanalytical chemistry》2013,405(22):7031-7039
The detection of hydrogen sulfide (H2S) by 2?+?1 resonance-enhanced multi-photon ionization (REMPI) and the application of H2S as a laser dopant for the detection of polar compounds in laser ion mobility (IM) spectrometry at atmospheric pressure were investigated. Underlying ionization mechanisms were elucidated by additional studies employing a drift cell interfaced to a time-of-flight mass spectrometer. Depending on the pressure, the primary ions H2S+, HS+, S+, and secondary ions, such as H3S+, were observed. The 2?+?1 REMPI spectrum of H2S near λ?=?302.5 nm was recorded at atmospheric pressure. Furthermore, the limit of detection and the linear range were established. In the second part of the work, H2S was investigated as an H2O analogous laser dopant for the ionization of polar substances by proton transfer. H2S exhibits a proton affinity (PA) similar to that of H2O, but a significantly lower ionization energy facilitating laser ionization. Ion-molecule reactions (IMR) of H3S+ with a variety of polar substances with PA between 754.6 and 841.6 kJ/mol were investigated. Representatives of different compound classes, including alcohols, ketones, esters, and nitroaromatics were analyzed. The IM spectra resulting from IMR of H3S+ and H3O+ with these substances are similar in structure, i.e., protonated monomer and dimer ion peaks are found depending on the analyte concentration. 相似文献
7.
1,3-Dipolar cycloaddition of various acyclic nitrones with 5-methylenehydantoin derivatives afforded new chiral spiroadducts in good yields. All the spirohydantoins were obtained through a regio- and stereospecific pathway, and the spirocarbon atom was linked to the isoxazolidine oxygen atom. A representative example of the reduction of the spirohydantoin 8 with Zn/AcOH led to the substituted 1,3-aminoalcohol hydantoin 20. 相似文献
8.
Mohsen K. Abou-Elregal Amira T. A. Mohamed Ahmed S. A. Youssef Magdy M. Hemdan Wael S. I. Abou-Elmagd 《合成通讯》2013,43(18):2347-2357
Reactions of 3-hyrazino-5,6-diphenyl-1,2,4-triazine with various carbonyl compounds such as ethyl acetoacetate, acetylacetone, benzoin, isatin, phthalic anhydride, phenyl isocyanate and acetic anhydride were discussed. Its reactions with α, β unsaturated compounds such as arylidinemalononitrile, diethyl acetylenedicarboxylate, dibenzylidine hydrazine were studied. These reactions led to the formation of various triazine and fused-triazine derivatives. The antitumor activity of the synthesized compounds was tested against HePG2 and MCF-7 cell lines. Some of the tested compounds were most active, whereas other compounds exhibited little or no activity. 相似文献
9.
Amel Souibgui Anne Gaucher Jérôme Marrot Flavien Bourdreux Faouzi Aloui Béchir Ben Hassine Damien Prim 《Tetrahedron》2014
New series of acridines and phenanthrolines have been prepared from β-chlorovinyl aldehydes and various aniline derivatives allowing the installation of valuable substituents, such as ketone, nitro or amino groups at the heterocyclic core. X-ray analyses confirmed the structures of acridines and phenanthrolines as well as the presence of partially hydrogenated rings and their crucial impact on the overall shape of the acridine-based architectures. 1H NMR revealed the helical behaviour of several acridine motives. Comparison of UV data between architectures and influence of number of partially hydrogenated rings is also described. 相似文献
10.
Arash Mollahosseini Shaghayegh Saadati Amira Abdelrasoul 《Journal of computational chemistry》2022,43(1):57-73
Despite advances in the field, hemoincompatibility remains a critical issue for hemodialysis (HD) as interactions between various human blood constituents and the polymeric structure of HD membranes results in complications such as activation of immune system cascades. Adding hydrophilic polymer structures to the membranes is one modification approach that can decrease the extent of protein adsorption. This study conducted molecular dynamics (MD) simulations to understand the interactions between three human serum proteins (fibrinogen [FB], human serum albumin, and transferrin) and common HD membranes in untreated and modified forms. Poly(aryl ether sulfone) (PAES) and cellulose triacetate were used as the common dialyzer polymers, and membrane modifications were performed with 2-hydroxymethyl methacrylate (HEMA) and poly (2-methoxyethyl acrylate) (PMEA), using polydopamine-assisted co-deposition. The MD simulations were used as the framework for binding energy simulations, and molecular docking simulations were also performed to conduct molecular-level investigations between the two modifying polymers (HEMA and PMEA) and FB. Each of the three proteins acted differently with the membranes due to their unique nature and surface chemistry. The simulations show PMEA binds less intensively to FB with a higher number of hydrogen bonds, which reflects PMEA's superior performance compared to HEMA. The simulations suggest PAES membranes could be used in modified forms for blood-contact applications as they reflect the lowest binding energy to blood proteins. 相似文献