全文获取类型
收费全文 | 626篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 552篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 39篇 |
物理学 | 51篇 |
出版年
2023年 | 9篇 |
2022年 | 24篇 |
2021年 | 18篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 13篇 |
2017年 | 14篇 |
2016年 | 21篇 |
2015年 | 17篇 |
2014年 | 18篇 |
2013年 | 36篇 |
2012年 | 41篇 |
2011年 | 65篇 |
2010年 | 22篇 |
2009年 | 32篇 |
2008年 | 56篇 |
2007年 | 51篇 |
2006年 | 28篇 |
2005年 | 31篇 |
2004年 | 17篇 |
2003年 | 14篇 |
2002年 | 13篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1993年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1984年 | 3篇 |
1981年 | 3篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1973年 | 4篇 |
1968年 | 2篇 |
1963年 | 1篇 |
1954年 | 2篇 |
1953年 | 1篇 |
1943年 | 1篇 |
1941年 | 1篇 |
1937年 | 2篇 |
1936年 | 1篇 |
1933年 | 1篇 |
1932年 | 1篇 |
1928年 | 1篇 |
1922年 | 1篇 |
排序方式: 共有651条查询结果,搜索用时 31 毫秒
121.
Let be a plane graph, and let be a colouring of its edges. The edge colouring of is called facial non-repetitive if for no sequence , , of consecutive edge colours of any facial path we have for all . Assume that each edge of a plane graph is endowed with a list of colours, one of which has to be chosen to colour . The smallest integer such that for every list assignment with minimum list length at least there exists a facial non-repetitive edge colouring of with colours from the associated lists is the facial Thue choice index of , and it is denoted by . In this article we show that for arbitrary plane graphs . Moreover, we give some better bounds for special classes of plane graphs. 相似文献
122.
Ilaria Bonaduce Leslie Carlyle Maria Perla Colombini Celia Duce Carlo Ferrari Erika Ribechini Paola Selleri Maria Rosaria Tiné 《Journal of Thermal Analysis and Calorimetry》2012,107(3):1055-1066
This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of
linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for
painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat
treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART
project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry
(GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to
elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature
helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised
and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and
non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid
(A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH4, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool
for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides
present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled
how oil pre-treatments produce binders with different physical–chemical qualities. 相似文献
123.
Károlyi BI Bösze S Orbán E Sohár P Drahos L Gál E Csámpai A 《Molecules (Basel, Switzerland)》2012,17(3):2316-2329
A series of novel functionalized mono-, bis- and tris-(S)-{[(2S,4R,8R)-8-ethyl-quinuclidin-2-yl](6-methoxyquinolin-4-yl)}methanamines including ferrocene-containing derivatives was obtained by the reaction of the precursor amine with a variety of acylation agents. Their in vitro antitumor activity was investigated against human leukemia (HL-60), human neuroblastoma (SH-SY5Y), human hepatoma (HepG2) and human breast cancer (MCF-7) cells by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT)-assay and the 50% inhibitory concentration (IC(50)) values were determined. Our data indicate that the precursor amine has no antitumor activity in vitro, but the bis-methanamines with ureido-, thioureido and amide-type linkers display attractive in vitro cytotoxicity and cytostatic effects on HL-60, HepG2, MCF-7 and SH-SY5Y cells. Besides 1H- and 13C-NMR methods the structures of the new model compounds were also studied by DFT calculations. 相似文献
124.
A series of stilbazolium dimers were synthesized and investigated as sterically demanding ligands targeting the norepinephrine transporter (NET). The environmentally sensitive fluorescence of the dyes enables their use as self-reporting ligands; binding to and displacement from NET can be monitored by fluorescence microscopy. 相似文献
125.
Michael addition reaction of α-branched aldehydes to β-nitroacrylates was successfully carried out by using a mixed catalyst consisting of a primary amino acid, L-phenylalanine, and its lithium salt to give β-formyl-β'-nitroesters having a quaternary carbon centre in good yields (up to 85%) with high enantioselectivity (up to 98% ee). By using benzyl β-nitroacrylates as Michael acceptors, the obtained β-formyl-β'-nitroesters were converted into various 4,4-disubstituted pyrrolidine-3-carboxylic acids including analogues of gabapentin (Neurotin(?)) in one step from the Michael adducts in high yields. 相似文献
126.
Phenyl cations are smoothly generated by the photoheterolytic cleavage of an Ar-LG bond (LG = leaving group). With the aim of evaluating the scope of the method, a series of 4-methoxy-2-(trimethylsilyl)phenyl derivatives (sulfonic, LG = MeSO(3) and CF(3)SO(3), phosphate, LG = (EtO)(2)(O)PO esters and the corresponding chloride) have been compared as probes for evaluating the leaving group ability. The photocleavage was a general reaction, with the somewhat surprising order (EtO)(2)(O)PO ~ Cl > CF(3)SO(3) > MeSO(3) (Φ = 0.50 to 0.16 in CF(3)CH(2)OH and lower values in MeCN-H(2)O). The ensuing reactions did not depend on the LGs but only on the structure of the phenyl cation (the silyl group tuned the triplet to singlet intersystem crossing and the electrophilicity) and on the medium (formation of a complex with water slowed the electrophilic reactions). 相似文献
127.
The classic constitutive equation relating fluid flux to a gradient in potential (pressure head plus gravitational energy)
through a porous medium was discovered by Darcy in the mid 1800s. This law states that the flux is proportional to the pressure
gradient. However, the passage of the fluid through the porous matrix may cause a local variation of the permeability. For
example, the flow may perturb the porous formation by causing particle migration resulting in pore clogging or chemically
reacting with the medium to enlarge the pores or diminish the size of the pores. In order to adequately represent these phenomena,
we modify the constitutive equations by introducing a memory formalism operating on both the pressure gradient–flux and the
pressure–density variations. The memory formalism is then represented with fractional order derivatives. We perform a number
of laboratory experiments in uniformly packed columns where a constant pressure is applied on the lower boundary. Both homogeneous
and heterogeneous media of different characteristic particle size dimension were employed. The low value assumed by the memory
parameters, and in particular by the fractional order, demonstrates that memory is largely influencing the experiments. The
data and theory show how mechanical compaction can decrease permeability, and consequently flux. 相似文献
128.
Biomineral formation is a common trait and prominent for soil Actinobacteria, including the genus Streptomyces. We investigated the formation of nickel-containing biominerals in the presence of a heavy-metal-resistant Streptomyces mirabilis P16B-1. Biomineralization was found to occur both in solid and liquid media. Minerals were identified with Raman spectroscopy and TEM-EDX to be either Mg-containing struvite produced in media containing no nickel, or Ni-struvite where Ni replaces the Mg when nickel was present in sufficient concentrations in the media. The precipitation of Ni-struvite reduced the concentration of nickel available in the medium. Therefore, Ni-struvite precipitation is an efficient mechanism for tolerance to nickel. We discuss the contribution of a plasmid-encoded nickel efflux transporter in aiding biomineralization. In the elevated local concentrations of Ni surrounding the cells carrying this plasmid, more biominerals occurred supporting this point of view. The biominerals formed have been quantified, showing that the conditions of growth do influence mineralization. This control is also visible in differences observed to biosynthetically synthesized Ni-struvites, including the use of sterile-filtered culture supernatant. The use of the wildtype S. mirabilis P16B-1 and its plasmid-free derivative, as well as a metal-sensitive recipient, S. lividans, and the same transformed with the plasmid, allowed us to access genetic factors involved in this partial control of biomineral formation. 相似文献
129.
Patricia Garcia-Herrera Helayne A. Maieves Erika N. Vega María Luisa Perez-Rodriguez Virginia Fernandez-Ruiz Amaia Iriondo-DeHond Maria Dolores del Castillo Maria Cortes Sanchez-Mata 《Molecules (Basel, Switzerland)》2022,27(17)
The feasibility of using dwarf kiwi fruits (Actinia arguta Miq.) as a healthy and sustainable food, compared to other types of commercial kiwi fruits, was evaluated in the present study. The overall antioxidant capacity of these fruits was assessed by either extraction-dependent methods (ABTS, ORAC) or the direct method called Quick, Easy, New, CHEap, Reproducible (QUENCHER) (DPPH, FRAP, Folin–Ciocalteu), applied for the first time to analyze kiwi fruits. With this methodology, all the molecules with antioxidant capacity are measured together in a single step, even those with high molecular weight or poor solubility in aqueous extraction systems, such as antioxidant dietary fiber. The effect of kiwi extracts on physiological and induced intracellular reactive oxygen species (ROS) production on IEC-6 cells was also analyzed, as well as total phenolic content (TPC) by Fast Blue BB, flavonols, hydroxycinnamic acids, and hydroxybenzoic acids. A. arguta fruits showed the highest values in all the antioxidant assays, being remarkably higher than the other kiwi species for Q-FRAP and Q-DPPH. Dwarf kiwi showed the highest potential in reducing physiological ROS and the highest values of TPC (54.57 mgGAE/g), being hydroxybenzoic acids the main phenolic family found (2.40 mgGAE/g). Therefore, dwarf kiwi fruits are a natural source of antioxidants compared to conventional kiwi fruits, being a sustainable and healthy alternative to diversify fruits in the diet. 相似文献
130.
Erika Galgoczi Monika Katko Fruzsina Reka Papp Robert Csiki Sara Csiha Annamaria Erdei Miklos Bodor Bernadett Ujhelyi Zita Steiber Ferenc Gyory Endre V. Nagy 《Molecules (Basel, Switzerland)》2023,28(1)
Orbital connective tissue expansion is a hallmark of Graves’ orbitopathy (GO). In moderate-to-severe active GO, glucocorticoids (GC) are the first line of treatment. Here we show that hydrocortisone (HC), prednisolone (P), methylprednisolone (MP), and dexamethasone (DEX) inhibit the hyaluronan (HA) production of orbital (OF) and dermal (DF) fibroblasts. HA production of GO OFs (n = 4), NON-GO OFs (n = 4) and DFs (n = 4) was measured by ELISA. mRNA expression of enzymes of HA metabolism and fibroblast proliferation was examined by RT-PCR and BrdU incorporation, respectively. After 24 h of GC treatment (1µM) HA production decreased by an average of 67.9 ± 3.11% (p < 0.0001) in all cell cultures. HAS2, HAS3 and HYAL1 expression in OFs also decreased (p = 0.009, p = 0.0005 and p = 0.015, respectively). Ten ng/mL PDGF-BB increased HA production and fibroblast proliferation in all cell lines (p < 0.0001); GC treatment remained effective and reduced HA production under PDGF-BB-stimulated conditions (p < 0.0001). MP and DEX reduced (p < 0.001, p = 0.002, respectively) PDGF-BB-induced HAS2 expression in OFs. MP and DEX treatment decreased PDGF-BB stimulated HAS3 expression (p = 0.035 and p = 0.029, respectively). None of the GCs tested reduced the PDGF-BB stimulated proliferation rate. Our results confirm that GCs directly reduce the HA production of OFs, which may contribute to the beneficial effect of GCs in GO. 相似文献