全文获取类型
收费全文 | 3082篇 |
免费 | 68篇 |
国内免费 | 9篇 |
专业分类
化学 | 2213篇 |
晶体学 | 31篇 |
力学 | 35篇 |
数学 | 318篇 |
物理学 | 562篇 |
出版年
2023年 | 25篇 |
2022年 | 114篇 |
2021年 | 87篇 |
2020年 | 53篇 |
2019年 | 58篇 |
2018年 | 36篇 |
2017年 | 38篇 |
2016年 | 81篇 |
2015年 | 67篇 |
2014年 | 81篇 |
2013年 | 180篇 |
2012年 | 180篇 |
2011年 | 206篇 |
2010年 | 113篇 |
2009年 | 126篇 |
2008年 | 136篇 |
2007年 | 177篇 |
2006年 | 161篇 |
2005年 | 139篇 |
2004年 | 108篇 |
2003年 | 101篇 |
2002年 | 88篇 |
2001年 | 62篇 |
2000年 | 50篇 |
1999年 | 28篇 |
1998年 | 23篇 |
1997年 | 21篇 |
1996年 | 36篇 |
1995年 | 39篇 |
1994年 | 18篇 |
1993年 | 30篇 |
1992年 | 24篇 |
1991年 | 19篇 |
1990年 | 30篇 |
1988年 | 13篇 |
1987年 | 19篇 |
1986年 | 25篇 |
1985年 | 26篇 |
1984年 | 18篇 |
1983年 | 25篇 |
1982年 | 14篇 |
1981年 | 20篇 |
1980年 | 19篇 |
1979年 | 17篇 |
1978年 | 29篇 |
1977年 | 14篇 |
1975年 | 14篇 |
1974年 | 15篇 |
1973年 | 15篇 |
1969年 | 14篇 |
排序方式: 共有3159条查询结果,搜索用时 15 毫秒
21.
One of the most intriguing aspects of synthetic chemistry is the interplay of numerous dependent and independent variables en route to achieve a successful, high-yielding chemical transformation. The experienced synthetic chemist will probe many of these variables during reaction development and optimization, which will routinely involve investigation of reaction temperature, solvent, stoichiometry, concentration, time, choice of catalyst, addition sequence or quenching conditions just to name some commonly addressed variables. Remarkably, little attention is typically given to the choice of reaction vessel material as the surface of common laboratory borosilicate glassware is, incorrectly, assumed to be chemically inert. When reviewing the scientific literature, careful consideration of the vessel material is typically only given during the use of well-known glass-etching reagents such as HF, which is typically only handled in HF-resistant, polyfluorinated polymer vessels. However, there are examples of chemical transformations that do not involve such reagents but are still clearly influenced by the choice of reaction vessel material. In the following review, we wish to condense the most significant examples of vessel effects during chemical transformations as well as observations of container-dependent stability of certain molecules. While the primary focus is on synthetic organic chemistry, relevant examples from inorganic chemistry, polymerization reactions, atmospheric chemistry and prebiotic chemistry are also covered.One of the most intriguing aspects of synthetic chemistry is the interplay of numerous dependent and independent variables en route to achieve a successful, high-yielding chemical transformation. 相似文献
22.
Klaudia Stando Ewa Korzeniewska Ewa Felis Monika Harnisz Sylwia Bajkacz 《Molecules (Basel, Switzerland)》2022,27(14)
Manure is a major source of soil and plant contamination with veterinary drugs residues. The aim of this study was to evaluate the uptake of 14 veterinary pharmaceuticals by parsley from soil fertilized with manure. Pharmaceutical content was determined in roots and leaves. Liquid chromatography coupled with tandem mass spectrometry was used for targeted analysis. Screening analysis was performed to identify transformation products in the parsley tissues. A solid-liquid extraction procedure was developed combined with solid-phase extraction, providing recoveries of 61.9–97.1% for leaves and 51.7–95.6% for roots. Four analytes were detected in parsley: enrofloxacin, tylosin, sulfamethoxazole, and doxycycline. Enrofloxacin was detected at the highest concentrations (13.4–26.3 ng g−1). Doxycycline accumulated mainly in the roots, tylosin in the leaves, and sulfamethoxazole was found in both tissues. 14 transformation products were identified and their distribution were determined. This study provides important data on the uptake and transformation of pharmaceuticals in plant tissues. 相似文献
23.
Angelika Wrzesiska Emilia Tomaszewska Katarzyna Ranoszek-Soliwoda Izabela Bobowska Jarosaw Grobelny Jacek Ulaski Aleksandra Wypych-Puszkarz 《Molecules (Basel, Switzerland)》2022,27(11)
At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl2-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl− counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl− counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems. 相似文献
24.
Lasse Jrgensen Cehofski Anders Kruse Alexander Nrgaard Alsing Benn Falch Sejergaard Jonas Ellegaard Nielsen Anders Schlosser Grith Lykke Sorensen Jakob Grauslund Bent Honor Henrik Vorum 《Molecules (Basel, Switzerland)》2022,27(11)
Aflibercept is a frequently used inhibitor of vascular endothelial growth factor (VEGF) in the treatment of macular edema following central retinal vein occlusion (CRVO). Retinal proteome changes following aflibercept intervention in CRVO remain largely unstudied. Studying proteomic changes of aflibercept intervention may generate a better understanding of mechanisms of action and uncover aspects related to the safety profile. In 10 Danish Landrace pigs, CRVO was induced in both eyes with an argon laser. Right eyes were treated with intravitreal aflibercept while left control eyes received isotonic saline water. Retinal samples were collected 15 days after induced CRVO. Proteomic analysis by tandem mass tag-based mass spectrometry identified a total of 21 proteins that were changed in content following aflibercept intervention. In retinas treated with aflibercept, high levels of aflibercept components were reached, including the VEGF receptor-1 and VEGF receptor-2 domains. Fold changes in the additional proteins ranged between 0.70 and 1.19. Aflibercept intervention resulted in a downregulation of pigment epithelium-derived factor (PEDF) (fold change = 0.84) and endoplasmin (fold change = 0.91). The changes were slight and could thereby not be confirmed with less precise immunohistochemistry and Western blotting. Our data suggest that aflibercept had a narrow mechanism of action in the CRVO model. This may be an important observation in cases when macular edema secondary to CRVO is resistant to aflibercept intervention. 相似文献
25.
Ewa Zaczyska Krzysztof Kaczmarek Janusz Zabrocki Jolanta Artym Micha Zimecki 《Molecules (Basel, Switzerland)》2022,27(11)
The core of Cyclolinopeptide A (CLA, cyclo(LIILVPPFF)), responsible for its high immunosuppressive activity, contains a Pro-Pro-Phe-Phe sequence. A newly synthesized cyclic tetrapeptide, cyclo(Pro-Pro-β3-HoPhe-Phe) (denoted as 4B8M) bearing the active sequence of CLA, was recently shown to exhibit a wide array of anti-inflammatory properties in mouse models. In this investigation, we demonstrate that the peptide significantly inhibits the replication of human adenovirus C serotype 5 (HAdV-5) and Herpes simplex virus type-1 (HSV-1) in epithelial lung cell line A-549, applying Cidofovir and Acyclovir as reference drugs. Based on a previously established mechanism of its action, we propose that the peptide may inhibit virus replication by the induction of PGE2 acting via EP2/EP4 receptors in epithelial cells. In summary, we reveal a new, antiviral property of this anti-inflammatory peptide. 相似文献
26.
27.
Agnieszka Nawirska-Olszaska Ewa Zaczyska Anna Czarny Joanna Kolniak-Ostek 《Molecules (Basel, Switzerland)》2022,27(9)
The aim of this study was to identify polyphenolic compounds contained in ethanol and water extracts of black alder (Alnus glutinosa L.) acorns and evaluate their anti-cancer and antimicrobial effects. The significant anti-cancer potential on the human skin epidermoid carcinoma cell line A431 and the human epithelial cell line A549 derived from lung carcinoma tissue was observed. Aqueous and ethanolic extracts of alder acorns inhibited the growth of mainly Gram-positive microorganisms (Staphylococcus aureus, Bacillus subtilis, Streptococcus mutans) and yeast-like fungi (Candida albicans, Candida glabrata), as well as Gram-negative (Escherichia coli, Citrobacter freundii, Proteus mirabilis, Pseudomonas aeruginosa) strains. The identification of polyphenols was carried out using an ACQUITY UPLC-PDA-MS system. The extracts were composed of 29 compounds belonging to phenolic acids, flavonols, ellagitannins and ellagic acid derivatives. Ellagitannins were identified as the predominant phenolics in ethanol and aqueous extract (2171.90 and 1593.13 mg/100 g DM, respectively) The results may explain the use of A. glutinosa extracts in folk medicine. 相似文献
28.
A new method to construct upper and lower bounds for the failure probability of a structure exposed to random excitations is presented. The method is based on an extension of the classical inclusion-exclusion series of Rice where the main idea is to take into consideration only realizations which are in the safe area at a number of previous instants of time. By a numerical example it is demonstrated that this method may lead to rather sharp bounds. 相似文献
29.
Ewa Katzenellenbogen Nina A. Kocharova Georgy V. Zatonsky Maria Bogulska Danuta Witkowska Aleksander S. Shashkov 《Journal of carbohydrate chemistry》2013,32(5):545-558
ABSTRACT Lipopolysaccharide (LPS) of Hafnia alvei 23 has an acid-labile O-specific polysaccharide (OPS) with a pentasaccharide-phosphate repeating unit containing D-Glc1P, D-GlcNAc, L-Fuc, 6-deoxy-D-talose (D-6dTal), 4-acetamido-4,6-dideoxy-D-glucose (D-Qui4NAc), and an O-acetyl group. A partially degraded OPS was obtained by hydrolysis of LPS with 0.25 M sodium acetate in aqueous 0.5% acetic acid. Fractionation of LPS on Sephadex G-200 in DOC buffer allowed isolation of long-chain LPS species which, together with OPS, were studied by methylation analysis, chemical degradations (O-deacetylation, dephosphorylation with 48% hydrofluoric acid, Smith degradation), and 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, NOESY, and H-detected 1H,13C heteronuclear single-quantum coherence (HSQC) experiments. The following structure of the repeating unit of OPS was established: 相似文献
30.
Andrzej Mianowski Izabela Baraniec-Mazurek Rafał Bigda 《Journal of Thermal Analysis and Calorimetry》2012,107(3):1155-1165
For dehydration of CaC2O4·H2O and thermal dissociation of CaCO3 carried out in Mettler Toledo TGA/SDTA-851e/STARe thermobalance similar experimental conditions was applied: 9–10 heating rates, q = 0.2, 0.5, 1, 2, 3, 6, 12, 24, 30, and 36 K min−1, for sample mass 10 mg, in nitrogen atmosphere (100 ml min−1) and in Al2O3 crucibles (70 μl). There were analyzed changes of typical TGA quantities, i.e., T, TG and DTG in the form of the relative rate of reaction/process intended to be analyzed on-line by formula (10). For comparative purposes, the relationship between experimental and equilibrium conversion degrees was used (for P = Pominus P = P^{{ominus}} ). It was found that the solid phase decomposition proceeds in quasi-equilibrium state and enthalpy of reaction is easily “obscured” by activation energy. For small stoichiometric coefficients on gas phase side (here: ν = 1) discussed decomposition processes have typical features of phenomena analyzable by known thermokinetic methods. 相似文献