全文获取类型
收费全文 | 1093篇 |
免费 | 21篇 |
国内免费 | 4篇 |
专业分类
化学 | 605篇 |
晶体学 | 3篇 |
力学 | 40篇 |
数学 | 311篇 |
物理学 | 159篇 |
出版年
2023年 | 10篇 |
2022年 | 28篇 |
2021年 | 33篇 |
2020年 | 40篇 |
2019年 | 23篇 |
2018年 | 26篇 |
2017年 | 19篇 |
2016年 | 40篇 |
2015年 | 28篇 |
2014年 | 36篇 |
2013年 | 60篇 |
2012年 | 79篇 |
2011年 | 94篇 |
2010年 | 69篇 |
2009年 | 51篇 |
2008年 | 54篇 |
2007年 | 61篇 |
2006年 | 56篇 |
2005年 | 55篇 |
2004年 | 50篇 |
2003年 | 24篇 |
2002年 | 26篇 |
2001年 | 21篇 |
2000年 | 12篇 |
1999年 | 16篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 9篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1968年 | 1篇 |
1932年 | 1篇 |
排序方式: 共有1118条查询结果,搜索用时 11 毫秒
41.
Konstantinos Petrotos Ioannis Giavasis Konstantinos Gerasopoulos Chrysanthi Mitsagga Chryssoula Papaioannou Paschalis Gkoutsidis 《Molecules (Basel, Switzerland)》2021,26(1)
Orange pomace (OP) is a solid waste produced in bulk as a byproduct of the orange juice industry and accounts for approximately 50% of the quantity of the fruits processed into juice. In numerous literature references there is information about diverse uses of orange pomace for the production of high-added-value products including production of natural antioxidant and antimicrobial extracts rich in polyphenols and flavonoids which can substitute the hazardous chemical antioxidants/antimicrobials used in agro-food and cosmetics sectors. In this work and for the first time, according to our knowledge, the eco-friendly aqueous vacuum microwave assisted extraction of orange pomace was investigated and optimized at real industrial scale in order to produce aqueous antioxidant/antimicrobial extracts. A Response Surface Optimization methodology with a multipoint historical data experimental design was employed to obtain the optimal values of the process parameters in order to achieve the maximum rates of extraction of OP total polyphenols and/or total flavonoids for economically optimum production at industrial scale. The three factors used for the optimization were: (a) microwave power (b) water to raw pomace ratio and (c) extraction time. Moreover, the effectiveness and statistical soundness of the derived cubic polynomial predictive models were verified by ANOVA. 相似文献
42.
Ioannis K. Stamos 《Journal of heterocyclic chemistry》1997,34(5):1487-1493
Treatment of compound 4 with trifluoroacetic anhydride under reflux in chlorobenzene underwent a tandem rearrangement to produce compound 5 . When the acetylated derivative of 4 , was treated with trifluoroacetic anhydride in the presence of Lewis acids produced two cis cyclized conformers 7a and 7b , presumably through the intermediate B . 相似文献
43.
James N. Tsoporis Ioannis-Alexandros Drosatos Sahil Gupta Hajera Amatullah Shehla Izhar Claudia C. dos Santos Vasileos Salpeas Angelos G. Rigopoulos Ioannis K. Toumpoulis Andreas S. Triantafyllis Eleftharios Sakadakis Nikolaos Kavantzas John C. Marshall Ioannis K. Rizos Thomas G. Parker 《Molecules (Basel, Switzerland)》2021,26(13)
DJ-1 was originally identified as an oncogene product while mutations of the gene encoding DJ-1/PARK7 were later associated with a recessive form of Parkinson’s disease. Its ubiquitous expression and diversity of function suggest that DJ-1 is also involved in mechanisms outside the central nervous system. In the last decade, the contribution of DJ-1 to the protection from ischemia-reperfusion injury has been recognized and its involvement in the pathophysiology of cardiovascular disease is attracting increasing attention. This review describes the current and gaps in our knowledge of DJ-1, focusing on its role in regulating cardiovascular function. In parallel, we present original data showing an association between increased DJ-1 expression and antiapoptotic and anti-inflammatory markers following cardiac and vascular surgical procedures. Future studies should address DJ-1’s role as a plausible novel therapeutic target for cardiovascular disease. 相似文献
44.
Ioannis Martakos Panagiota Katsianou Georgios Koulis Elvira Efstratiou Eleni Nastou Stylianos Nikas Marilena Dasenaki Michalis Pentogennis Nikolaos Thomaidis 《Molecules (Basel, Switzerland)》2021,26(23)
In this study, an overall survey regarding the determination of several bioactive compounds in olive fruit is presented. Two methodologies were developed, one UPLC-Q-TOF-MS method for the determination of olive fruit phenolic compounds and one HPLC-DAD methodology targeting the determination of pigments (chlorophylls and carotenoids), tocopherols (α-, β, -γ, δ-) and squalene. Target and suspect screening workflows were developed for the thorough fingerprinting of the phenolic fraction of olives. Both methods were validated, presenting excellent performance characteristics, and can be used as reliable tools for the monitoring of bioactive compounds in olive fruit samples. The developed methodologies were utilized to chemical characterize the fruits of the Kolovi olive variety, originating from the island of Lesvos, North Aegean Region, Greece. Twenty-five phenolic compounds were identified and quantified in Kolovi olives with verbascoside, hydroxytyrosol, oleacein and oleomissional found in significantly high concentrations. Moreover, 12 new bioactive compounds were identified in the samples using an in-house suspect database. The results of pigments analysis suggested that Kolovi variety should be characterized as low pigmentation, while the tocopherol and squalene content was relatively high compared to other olive varieties. The characterization of Kolovi olive bioactive content highlighted the high nutritional and possible economic value of the Kolovi olive fruit. 相似文献
45.
Christina Tzitzoglaki Antonios Drakopoulos Athina Konstantinidi Ioannis Stylianakis Marianna Stampolaki Antonios Kolocouris 《Tetrahedron》2019,75(34):130408
Primary tert-alkyl amines include analogues of amantadine, a fragment commonly linked to pharmacophoric groups to enhance biological activity. The preparation of primary tert-alkyl amines is considered to be a difficult problem. Four synthetic procedures, some of which have been previously reported for the synthesis of amines with primary (RCH2NH2) or secondary (RR'CHNH2) alkyl and/or aryl groups, were tested for the synthesis of primary tert-alkyl amines (RR′R″CNH2) in aliphatic series including adamantane adducts. These procedures included the formation and reduction of tert-alkyl azides, the Ritter reaction in standard and modified conditions, the addition of organometallic reagents to N-tert-butyl sulfinyl ketimines and one-pot reactions between nitriles and organometallic reagents in the presence of a Lewis acid, Τi(iPrO)4 or CeCl3. These synthetic routes are unexplored for primary tert-alkyl amines. Studies on the synthetic routes for primary tert-alkyl amines are currently lacking. The reaction conditions and substrate limitations were studied for each procedure, with the first procedure being the most general and applicable also for compounds bearing bulky adducts. 相似文献
46.
47.
Molecular dynamics atomistic simulations in the canonical ensemble (NVT-MD) have been used to investigate the "Local Density Inhomogeneities and their Dynamics" in pure supercritical water. The simulations were carried out along a near-critical isotherm (Tr = T/Tc = 1.03) and for a wide range of densities below and above the critical one (0.2 rho(c) - 2.0 rho(c)). The results obtained reveal the existence of significant local density augmentation effects, which are found to be sufficiently larger in comparison to those reported for nonassociated fluids. The time evolution of the local density distribution around each molecule was studied in terms of the appropriate time correlation functions C(Delta)rhol(t). It is found that the shape of these functions changes significantly by increasing the density of the fluid. Finally, the local density reorganization times for the first and second coordination shell derived from these correlations exhibit a decreasing behavior by increasing the density of the system, signifying the density effect upon the dynamics of the local environment around each molecule. 相似文献
48.
Nikos Karanikolopoulos Ioannis Choinopoulos Marinos Pitsikalis 《Journal of polymer science. Part A, Polymer chemistry》2020,58(11):1582-1600
A series of well-defined poly{dl -lactide-b-[oligo(ethylene glycol) methyl ether (meth)acrylate)]} (PDLLA-b-POEG[M]A) functional amphiphilic diblock copolymers was synthesized by employing a multistep procedure involving: (a) ring-opening polymerization of dl -lactide using n-decanol and stannous octoate as the initiating system, (b) esterification reaction of the PDLLA hydroxyl end groups with 2-bromoisobutyryl bromide, (c) atom transfer radical polymerization of OEG(M)A with the newly created bromoisobutyryl initiating site, and (d) incorporation of biotin or folic acid at the POEGA chain ends using click chemistry. The products were characterized by NMR spectroscopy and SEC analysis. The aggregation behavior of the synthesized block copolymers was investigated by dynamic light scattering at 25°C in aqueous solutions. The hydrophobic model compounds Nile red and pyrene were efficiently incorporated into the copolymer aggregates in aqueous solutions. High partition coefficient values were determined by fluorescence spectroscopy. 相似文献
49.
DFT calculations of 1H NMR chemical shifts, using various functionals and basis sets, the conductor-like polarizable continuum model and discrete solute-solvent hydrogen bond interactions have been used to derive the solution structures of methyl salicylate and methyl 2,5-dihydroxybenzoate. We demonstrate that very good agreement between experimental and computed 1H NMR chemical shifts can be obtained for various basis sets. The DFT structures in solution were compared with the recently reported X-ray structure, solved by the crystalline-sponge method, of the methyl salicylate and the single-crystal X-ray structure of methyl 2,5-dihydroxybenzoate. It is demonstrated that the information provided by 1H NMR chemical shifts about the solution structure is significantly more precise than that obtained by the single-crystal X-ray and the crystalline-sponge methods. 相似文献
50.
Trans-hydrogen-bond deuterium isotope effects of Watson-Crick A:U and A:T base pairs of 10 homologous RNA and DNA duplexes are compared. The isotope effect at 13C2 of adenosine residues due to deuterium/protium substitution at the imino H3 site, 2hDelta13C2, is larger in RNA than in DNA. The virtually consistent larger isotope effects in RNA suggest that the N1...N3 hydrogen bonds of A:U base pairs of RNA are stronger than those of the A:T base pairs of DNA. 相似文献