全文获取类型
收费全文 | 1092篇 |
免费 | 46篇 |
国内免费 | 2篇 |
专业分类
化学 | 897篇 |
晶体学 | 8篇 |
力学 | 19篇 |
数学 | 107篇 |
物理学 | 109篇 |
出版年
2024年 | 1篇 |
2023年 | 15篇 |
2022年 | 58篇 |
2021年 | 64篇 |
2020年 | 42篇 |
2019年 | 45篇 |
2018年 | 32篇 |
2017年 | 23篇 |
2016年 | 59篇 |
2015年 | 55篇 |
2014年 | 42篇 |
2013年 | 64篇 |
2012年 | 76篇 |
2011年 | 94篇 |
2010年 | 53篇 |
2009年 | 46篇 |
2008年 | 59篇 |
2007年 | 61篇 |
2006年 | 55篇 |
2005年 | 50篇 |
2004年 | 29篇 |
2003年 | 27篇 |
2002年 | 20篇 |
2001年 | 3篇 |
2000年 | 11篇 |
1999年 | 7篇 |
1998年 | 9篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1981年 | 1篇 |
1911年 | 1篇 |
排序方式: 共有1140条查询结果,搜索用时 15 毫秒
11.
Brunella Cappello Clelia Di Maio Maria Iervolino 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):251-257
The interactions of Bendazac, a topical non-steroidal anti-inflammatory drug, with-cyclodextrin, hydroxypropyl--cyclodextrin and -cyclodextrinwere investigated to evaluate possibilities to improve the drug's poor water solubilityand eventually to enhance the topical delivery of Bendazac. Phase solubility studiesdemonstrated the ability of the selected cyclodextrins to complex with Bendazac andincrease drug solubility. The amount of solubilized Bendazac increased linearly withthe addition of each cyclodextrin according toAL type plots. 13C-NMR studiesshowed that the Bendazac A-ring was included in the cavity of the three cyclodextrins.The -cyclodextrin was also able to include the B-ring of Bendazac, forminga complex where one drug molecule fitted into two cyclodextrin molecules. Equimolarsolid systems of the drug with each cyclodextrin carrier were prepared using varioustechniques (physical mixing, spray-drying and freeze-drying). The results of differential scanning calorimetry and Fourier transform infrared analysis, performed on the solid systems, demonstrated that freeze-dried and spray-dried products had a high degree of amorphization and agreed with the hypothesis of the existence of drug–cyclodextrin interaction in the solid state. The cyclodextrins tested were able to improve the dissolution of Bendazac. The dissolution profile of the drug was also affected by the physico-chemical properties of each solid system, the freeze-dried products being the most rapidly dissolving forms. 相似文献
12.
Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds. 相似文献
13.
Angelini N Micali N Mineo P Scamporrino E Villari V Vitalini D 《The journal of physical chemistry. B》2005,109(39):18645-18651
Changes in the UV-vis spectra and induced circular dichroism (ICD) signals observed, in correspondence with the porphyrin Soret region, for aqueous solutions of achiral 5,10,15,20-tetrakis{p-[omega-methoxy poly(oxy-ethylene)]phenyl}porphyrin cobalt (II) (Co-P) and aromatic alpha-L-amino acids (Trp and Phe) give direct evidence for the coordination between the Co-P and amino acids. Considering that Co-P, besides the Co atom (one-fixation-point system), does not contain in the molecule active ligand groups and that no ICD signals have been observed in the case of Co-P/Ala, it has been concluded that hydrophobic interactions or stacking interactions between the aromatic rings of the porphyrin and those of Trp or Phe, acting as further amino acid (AA) fixation points, can strongly reduce the mobility of the chiral guest, thus permitting the generation of ICD signals. The effects of changes of both pH (in the range 2-9) and amino acid structure on the ICD phenomenon have also been investigated. In particular, the following have been observed: (i) strong ICD signals for all of the Co-P/N-acetyl amino acid aqueous solutions at pH 7, (ii) an unexpected ICD band with a bisignate form for the Co-P/Ala solution at pH 9 after long aging, and (iii) an opposite ICD signal when alpha-D-Phe and alpha-D-Trp enantiomers have been used. The data reported in this paper show how the binding mechanism between receptor and AAs changes by modulating properly the pH or the molecular structures and indicate that in these aqueous solutions the coordination Co-N is not the fundamental mechanism giving rise to the formation of the complexes and that the binding can be driven by hydrophobic interactions. These occurrences, through the analysis of the spectroscopic response (and, in particular, the form of the ICD band), can allow the recognition of AAs. 相似文献
14.
15.
16.
This paper presents the application of the eMergy evaluation, introduced by H.T. Odum as an efficient methodology of environmental accounting. The results of this analysis are a part of a wider sustainability assessment for the Province of Venice realized in 2003. Within a territorial sustainability analysis, it is necessary to implement an environmental accounting method, which is able: to precisely consider the boundaries of the investigated system (spatial scale); to arbitrarily separate the life of the investigated system into periods (temporal scale); to account for both economic and natural support to a given territorial system in order to implement a sustainable management of resources; to assess all the items supporting the system on the basis of a physical unit that is objective (while the traditional economic evaluation method is based on individual preferences, hence it is subjective). The Province of Venice is a very complex system due, on one hand, to the heavy and consolidated presence of industrial activity since the beginning of the 20th century and, on the other hand, to the principal natural ecosystem which characterizes it: the lagoon, the largest wetland in the Mediterranean Sea. The role of the lagoon, as a provider of resources and services is represented by the analysis of two aspects: the lagoon as an ecosystem on the basis of the evaluation of all flows that cyclically support its biotic activity and the lagoon as a productive system on the basis of the contribution of both natural and "economic" inputs that support human activity. In particular, the case of clam fishing will be presented to put on evidence the importance of natural inputs that are systematically neglected by the traditional accounting methodologies. 相似文献
17.
Domenici V Geppi M Veracini CA Zakharov AV 《The journal of physical chemistry. B》2005,109(39):18369-18377
In this work, the rotational-diffusion coefficients D(parallel) and D(perpendicular) for the ferroelectric smectogen (+)-(S)-4-[4'-(1-methylheptyloxy)] biphenyl 4-(10-undecenyloxy)benzoate have been studied by means of 2H NMR spectroscopy in the smectic C phase, using a new theoretical approach (Domenici,V.; Geppi, M.; Veracini, C. A. Chem. Phys. Lett. 2003, 382, 518). The analysis of spin-lattice relaxation times has been performed in terms of the diffusional constant and the activation energy of the internal and overall molecular-reorientational motions, and the results are compared to the smectic A (SmA) phase. Moreover, from the 2H NMR data in the SmA phase, the dielectric permittivity and the dielectric relaxation time functions are investigated using a theoretical approach. The longitudinal and transverse components of the real Rchigammaomega and imaginary chigammaomega (gamma = parallel, perpendicular) parts of the complex susceptibility tensor and the nematic-like rotational-viscosity coefficients, lambda2 and lambda5, are calculated. 相似文献
18.
Franco L Mazzoni M Corvaja C Gubskaya VP Berezhnaya LSh Nuretdinov IA 《Chemical communications (Cambridge, England)》2005,(16):2128-2130
After pulsed photoexcitation of a new fullerene-linked bisnitroxide, a well resolved transient EPR spectrum is detected which is assigned to an excited quintet spin state generated by spin coupling of the nitroxides and the fullerene excited triplet. 相似文献
19.
Valentina Gazzola Pietro Grisoli Valeria Amendola Giacomo Dacarro Carlo Mangano Piersandro Pallavicini Antonio Poggi Silvia Rossi Barbara Vigani Angelo Taglietti 《Molecules (Basel, Switzerland)》2022,27(17)
In this paper, we report on the preparation of Imidazole-functionalized glass surfaces, demonstrating the ability of a dinuclear Cu(II) complex of a macrocyclic ligand to give a “cascade” interaction with the deprotonated forms of grafted imidazole moieties. In this way, we realized a prototypal example of an antimicrobial surface based on a supramolecular approach, obtaining a neat microbicidal effect using low amounts of the described copper complex. 相似文献
20.
Cristbal Balada Valentina Díaz Mnica Castro Macarena Echeverría-Bugueo María Jos Marchant Leda Guzmn 《Molecules (Basel, Switzerland)》2022,27(17)
Microsorum scolopendia (MS), which grows on the Chilean island of Rapa Nui, is a medicinal fern used to treat several diseases. Despite being widely used, this fern has not been deeply investigated. The aim of this study was to perform a characterization of the polyphenolic and flavonoid identity, radical scavenging, antimicrobial, and anti-inflammatory properties of MS rhizome and leaf extracts (RAE and HAE). The compound identity was analyzed through the reversed-phase high-performance liquid chromatography (RP-HPLC) method coupled with mass spectrometry. The radical scavenging and anti-inflammatory activities were evaluated for DPPH, ORAC, ROS formation, and COX inhibition activity assay. The antimicrobial properties were evaluated using an infection model on Human Dermal Fibroblast adult (HDFa) cell lines incubated with Staphylococcus aureus and Staphylococcus epidermidis. The most abundant compounds were phenolic acids between 46% to 57% in rhizome and leaf extracts, respectively; followed by flavonoids such as protocatechic acid 4-O-glucoside, cirsimaritin, and isoxanthohumol, among others. MS extract inhibited and disaggregated the biofilm bacterial formed and showed an anti-inflammatory selective property against COX-2 enzyme. RAE generated a 64% reduction of ROS formation in the presence of S. aureus and 87.35% less ROS in the presence of S. epidermidis on HDFa cells. MS has great therapeutic potential and possesses several biological properties that should be evaluated. 相似文献