全文获取类型
收费全文 | 631篇 |
免费 | 29篇 |
国内免费 | 10篇 |
专业分类
化学 | 465篇 |
晶体学 | 3篇 |
力学 | 21篇 |
数学 | 61篇 |
物理学 | 120篇 |
出版年
2023年 | 8篇 |
2022年 | 39篇 |
2021年 | 60篇 |
2020年 | 24篇 |
2019年 | 33篇 |
2018年 | 30篇 |
2017年 | 13篇 |
2016年 | 43篇 |
2015年 | 26篇 |
2014年 | 34篇 |
2013年 | 53篇 |
2012年 | 56篇 |
2011年 | 46篇 |
2010年 | 29篇 |
2009年 | 27篇 |
2008年 | 35篇 |
2007年 | 21篇 |
2006年 | 12篇 |
2005年 | 12篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 9篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1987年 | 3篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有670条查询结果,搜索用时 484 毫秒
81.
Mohamad Akbar Ali 《Molecular physics》2013,111(20):2149-2158
Cyclic [n]paraphenyleneacetylenes ([n]CPPAs) are potentially useful compounds for molecular electronics. In this article, a homodesmotic reaction scheme coupled with density functional theory has been used to estimate theoretically strain energies and heats of formation of [n]CPPAs. Calculations have been done for a series of [n]CPPAs, containing up to ten phenylacetylene units. Strain energies of [n]CPPAs decrease, while heats of formation increase steadily with the increase in the number of phenylacetylene units using homodesmotic reaction schemes. B3LYP and mPW1PW91 functionals have been used with the Pople basis set 6-31G* to analyze the trends. The results are sensitive to the scheme of homodesmotic reaction chosen, thereby necessitating careful chemical consideration before spending considerable computational resources for higher [n]CPPAs not considered here. Computational estimates for the ring diameter of [n]CPPAs and absolute entropy have also been obtained here. The HOMO-LUMO gaps of the belt shaped [n]CPPAs show an odd–even difference. In addition, the HOMOs of the [3]CPPA, [5]CPPA, [7]CPPA and [9]CPPA are doubly degenerate. 相似文献
82.
83.
Sannay Mohamad 《Journal of Difference Equations and Applications》2013,19(6):559-575
A novel method called semi-discretization is employed in the formulation of discrete-time analogues of nonlinear delayed differential equations modelling cellular neural networks. The dynamical characteristics of the discrete-time analogues are studied. When the network parameters satisfy certain sufficient conditions which are independent of the delays, the discrete-time analogues for any choice on the discretization step-size are shown to be globally exponentially stable. The sufficient conditions are obtained by employing an appropriate form of Lyapunov sequences and these conditions correspond to those which have been obtained in the literature for the global exponential stability of continuous-time delayed cellular neural networks. Several examples and computer simulations are given to support our results and to demonstrate some of the advantages of the discrete-time analogues in numerically simulating their continuous-time counterparts. 相似文献
84.
A method using high-performance liquid chromatography with diode array detection (HPLC-DAD) as a powerful separation technique has been developed for the simultaneous determination of the four flavonols rutin, quercetin, kaempferol and isorhamnetin in food supplements and pharmaceutical formulations. The chromatographic separation was achieved in 36?min using a Symmetry C18 column (250?×?3?mm; 5?µm) as the stationary phase and a mixture of methanol, acetonitrile, and pH 2.5 aqueous acetic acid as the mobile phase in gradient elution mode. The analytical wavelengths were 256?nm for rutin, quercetin and isorhamnetin, and 368?nm for kaempferol. An ultrasound-assisted extraction protocol was performed using methanol as solvent. The detection and quantification limits were lower than 0.03?µg mL?1 and 0.08?µg mL?1, respectively. The inter-day and intra-day precisions were less than 4.8 and 5.1%, respectively, and the average recoveries were in the range from 96 to 107%. The method was applied for the determination of the studied flavonols in food supplements and pharmaceutical preparations. The satisfactory recovery values demonstrate the potential of the developed method for the determination of the analytes in these samples. In addition, the method is suitable for routine quality control due its ease of operation. 相似文献
85.
In this study the antioxidant and cytotoxicity activity of the Adonidia merrillii fruits were investigated using different solvent polarities (methanol, ethyl acetate and water). The results showed that the total phenolic and flavonoid contents of the methanolic extract was higher compare with other extract with respective values of 17.80 ± 0.45 mg gallic acid equivalents/g dry weight (DW) and 5.43 ± 0.33 mg rutin equivalents/g DW. Beside that The RP-HPLC analyses indicated the presence of gallic acid, pyrogallol, caffeic acid, vanillic acid, syringic acid, naringin and rutin. In the DPPH, NO2 and ABTS scavenging assays, the methanolic extract exhibited higher antioxidant activity as compared to the ethyl acetate and water extracts. The extracts exhibited moderate to weak cytotoxic activity in the assays using human hepatocytes (Chang liver cells) and NIH/3T3 (fibroblasts cell) cell lines. The findings showed the Adonidia merrillii fruit extracts to possess considerable antioxidant and cytotoxicity properties. The fruit, therefore, is a potential candidate for further work to discover antioxidant and cytotoxic drugs from natural sources. 相似文献
86.
Conductivity studies of plasticized anhydrous PEO-KOH alkaline solid polymer electrolyte 总被引:1,自引:0,他引:1
Polyethylene oxide (PEO)–potassium hydroxide (KOH)-based alkaline solid polymer electrolyte films have been prepared by using
methanol as solvent. The highest room temperature ionic conductivity of (2.1 ± 0.5) × 10−8 S cm−1 was achieved for the composition of 70 wt% PEO:30 wt% KOH. The addition of plasticizer, ethylene carbonate, propylene carbonate,
or polyethylene glycol to the highest conductivity of PEO–KOH system helps to increase the ambient ionic conductivity to the
order of 10−6–10−4 S cm−1. The log σ vs 1/T plot of PEO–KOH showed a small conductivity decrease at 50–60 °C range. The small decrease and the hysteresis that occur
during the heating–cooling cycle was overcome by the presence of the plasticizer. X-ray diffraction observation supports the
conductivity results. 相似文献
87.
Dr. Peiyu Ge Dr. Mohamad Hojeij Dr. Micheál D. Scanlon Prof. Hubert H. Girault 《Chemphyschem》2020,21(24):2630-2633
H2 may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H2 production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc+) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc+ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc+ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO2 (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc+ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger. 相似文献
88.
89.
Mohamad Hasan Mohamadzadeh Moghadam Sina Sabury Mohsen Moazzami Gudarzi Farhad Sharif 《Journal of polymer science. Part A, Polymer chemistry》2014,52(11):1545-1554
Graphene oxide (GO)–polyaniline (PANI) composite is synthesized by in situ polymerization of aniline in the presence of GO as oxidant, resulting in highly crystalline and conductive composite. Fourier transform infrared spectrum confirms aniline polymerization in the presence of GO without using conventional oxidants. Scanning electron microscopic images show the formation of PANI nanofibers attached to GO sheets. X‐ray diffraction (XRD) patterns indicate the presence of highly crystalline PANI. The sharp peaks in XRD pattern suggest GO sheets not only play an important role in the polymerization of aniline but also in inducing highly crystalline phase of PANI in the final composite. Electrical conductivity of doped GO–PANI composite is 582.73 S m?1, compared with 20.3 S m?1 for GO–PANI obtained by ammonium persulfate assisted polymerization. The higher conductivity appears to be the result of higher crystallinity and/or chemical grafting of PANI to GO, which creates common conjugated paths between GO and PANI. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1545–1554 相似文献
90.
Considering the importance of silylene ligands in transition metal-mediated catalytic reactions, we have scrutinized eight novel monodentate ( 1 – 4 ) and bidentate ( 1 ′ - 4 ′ ) derivatives of 2,5-diX-cyclopentasilylene-2,4-dienes (X = NH2, OH, PH2, and SH), at M06/6-311++G** level of theory. To probe the complexation ability of our scrutinized silylene ligands with Rh atom ( 1 Rh - 4 Rh and 1 ′ Rh - 4 ′ Rh , respectively), thermodynamic and structural parameters such as complexation energy (ΔECom), singlet-triplet energy gap (ΔEs-t), bond length, along with NBO and atoms in molecules analyses are provided. In going from less electron donating groups (EDGs) to more EDGs (NH2 > OH > PH2 > SH), the σ -donor strength and ligand flexibility increase. Structures 1 and 1 ′ turn out as the most nucleophilic species for showing the highest nucleophilicity (N = 5.47 and 5.40 eV, respectively). Furthermore, they exhibit the highest proton affinity values (PA = 271.46 and 271.23 kcal/mol, respectively). The results indicate that bidentate coordination mode of silylene leads to a stronger Si-Rh complex. The overall orders of σ -donation ability for monodentate and bidentate silylene ligands are 1 > 2 > 3 > 4 and 1 ′ > 2 ′ > 3 ′ > 4 ′ , respectively. 相似文献