全文获取类型
收费全文 | 886篇 |
免费 | 37篇 |
国内免费 | 3篇 |
专业分类
化学 | 582篇 |
晶体学 | 6篇 |
力学 | 20篇 |
数学 | 81篇 |
物理学 | 237篇 |
出版年
2022年 | 17篇 |
2021年 | 31篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 21篇 |
2017年 | 15篇 |
2016年 | 32篇 |
2015年 | 32篇 |
2014年 | 35篇 |
2013年 | 56篇 |
2012年 | 53篇 |
2011年 | 70篇 |
2010年 | 56篇 |
2009年 | 49篇 |
2008年 | 43篇 |
2007年 | 46篇 |
2006年 | 33篇 |
2005年 | 31篇 |
2004年 | 27篇 |
2003年 | 11篇 |
2002年 | 24篇 |
2001年 | 20篇 |
2000年 | 20篇 |
1999年 | 15篇 |
1998年 | 15篇 |
1997年 | 9篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 14篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1926年 | 1篇 |
1924年 | 2篇 |
排序方式: 共有926条查询结果,搜索用时 515 毫秒
911.
Roberto Luiz Andrade HaidukeAuthor Vitae Ubirajara Pereira Rodrigues-FilhoAuthor Vitae 《Polyhedron》2011,30(8):1396-1403
We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H2O, NH3, imidazole and CH3CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH3CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH3CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty π∗ orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. 相似文献
912.
Velvadapu V Paul T Wagh B Glassford I DeBrosse C Andrade RB 《The Journal of organic chemistry》2011,76(18):7516-7527
Novel sources of antibiotics are required to address the serious problem of antibiotic resistance. Telithromycin (2) is a third-generation macrolide antibiotic prepared from erythromycin (1) and used clinically since 2004. Herein we report the details of our efforts that ultimately led to the total synthesis of (-)-4,8,10-tridesmethyl telithromycin (3) wherein methyl groups have been replaced with hydrogens. The synthesis of desmethyl macrolides has emerged as a novel strategy for preparing bioactive antibiotics. 相似文献
913.
Tôrres AR Lyra Wda S de Andrade SI Andrade RA da Silva EC Araújo MC Gaião Eda N 《Talanta》2011,84(3):601-606
This work proposes the use of digital image-based method for determination of total acidity in red wines by means of acid-base titration without using an external indicator or any pre-treatment of the sample. Digital images present the colour of the emergent radiation which is complementary to the radiation absorbed by anthocyanines present in wines. Anthocyanines change colour depending on the pH of the medium, and from the variation of colour in the images obtained during titration, the end point can be localized with accuracy and precision. RGB-based values were employed to build titration curves, and end points were localized by second derivative curves. The official method recommends potentiometric titration with a NaOH standard solution, and sample dilution until the pH reaches 8.2-8.4. In order to illustrate the feasibility of the proposed method, titrations of ten red wines were carried out. Results were compared with the reference method, and no statistically significant difference was observed between the results by applying the paired t-test at the 95% confidence level. The proposed method yielded more precise results than the official method. This is due to the trivariate nature of the measurements (RGB), associated with digital images. 相似文献
914.
The Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence has been used in many applications of magnetic resonance imaging (MRI) and low-resolution NMR (LRNMR) spectroscopy. Recently, CPMG was used in online LRNMR measurements that use long RF pulse trains, causing an increase in probe temperature and, therefore, tuning and matching maladjustments. To minimize this problem, the use of a low-power CPMG sequence based on low refocusing pulse flip angles (LRFA) was studied experimentally and theoretically. This approach has been used in several MRI protocols to reduce incident RF power and meet the specific absorption rate. The results for CPMG with LRFA of 3π/4 (CPMG135), π/2 (CPMG90) and π/4 (CPMG45) were compared with conventional CPMG with refocusing π pulses. For a homogeneous field, with linewidth equal to Δυ = 15 Hz, the refocusing flip angles can be as low as π/4 to obtain the transverse relaxation time (T2) value with errors below 5%. For a less homogeneous magnetic field, Δυ = 100 Hz, the choice of the LRFA has to take into account the reduction in the intensity of the CPMG signal and the increase in the time constant of the CPMG decay that also becomes dependent on longitudinal relaxation time (T1). We have compared the T2 values measured by conventional CPMG and CPMG90 for 30 oilseed species, and a good correlation coefficient, r = 0.98, was obtained. Therefore, for oilseeds, the T2 measurements performed with π/2 refocusing pulses (CPMG90), with the same pulse width of conventional CPMG, use only 25% of the RF power. This reduces the heating problem in the probe and reduces the power deposition in the samples. 相似文献
915.
Ferreres F Gil-Izquierdo A Vinholes J Grosso C Valentão P Andrade PB 《Rapid communications in mass spectrometry : RCM》2011,25(6):700-712
The use of mass spectrometry (MS) coupled to liquid chromatography (LC) as working tool for the study of the C-glycosyl flavones acylated with aliphatic and aromatic acids has allowed the tentative characterization of these compounds in Spergularia rubra and the establishment of the position of the acylation on the sugar moiety of the C-glycosylation by use of MS data. The combination of retention time (Rt), ultraviolet (UV) and MS(n) data of the compounds revealed their C-glycosyl flavone nature, being luteolin, apigenin and chrysoeriol derivatives. Ten non-acylated flavones were identified, from which six are described for the first time (one 7-O-glycosyl-6,8-diC-glycosyl flavone, four 6,8-diC-glycosyl flavones and one 2"-O-glycosyl-6-C-glycosyl flavone). Twenty-six acylated derivatives were also found for the first time. These compounds are grouped in three classes, namely, C-glycosyl flavones acylated with aliphatic acids, with aromatic acids or with a mixed acylation. The first group is characterized by the presence of one 6,8-diC-(acetyl)glycosyl flavone, four 6,8-diC-(malonyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(malonyl)glycosyl flavones, while in the second one twelve 6,8-diC-(acyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(acyl)glycosyl flavones are described. The last class contained five 6,8-diC-(malonyl,acyl)glycosyl flavones. No previous work has described the presence of C-glycosyl flavones acylated with aliphatic acids in this genus. 相似文献
916.
Tarley CR Andrade FN de Oliveira FM Corazza MZ de Azevedo LF Segatelli MG 《Analytica chimica acta》2011,703(2):145-151
A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb(2+) ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb(2+) ions as template, tetraethoxysilane as reticulating agent and 2,2'-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L(-1)), eluent (HNO(3)) concentration (0.5 mol L(-1)) and preconcentration flow rate (4.0 mL min(-1)), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L(-1) (r=0.999) with limit of detection of 0.75 μg L(-1); the precision (repeatability) calculated as relative standard deviation (n=10) was 5.0 and 3.6% for Pb(2+) concentration of 10.0 and 60.0 μg L(-1), respectively. From on-line breakthrough curve, column capacity was 3.5 mg g(-1). Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min(-1), respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb(2+)/Cd(2+), Pb(2+)/Cu(2+) and Pb(2+)/Zn(2+). The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb(2+) than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb(2+) determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results. 相似文献
917.
Cliciane Guadalupe de Jesus Cristiane Maria Sampaio Forte Karen Wohnrath Christiana Andrade Pessôa Janete Elisa de Sá Soares Sérgio Toshio Fujiwara Pedro de Lima‐Neto Adriana Nunes Correia 《Electroanalysis》2011,23(8):1814-1820
A (SiPy+Cl?/CuTsPc)5 layer‐by‐layer film was employed for the electroanalytical determination of promethazine hydrochloride in BR buffer pH 5.0 with peaks at 0.48 and 0.79 V. After optimisation of the square‐wave parameters (f=100 s?1, a=40 mV and ΔEs=2 mV), the peak at 0.79 V was used for quantification and a detection limit of 8.71×10?9 mol L?1 and a quantification limit of 9.31×10?8 were calculated. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples, without any preliminary treatment. 相似文献
918.
Blends of biodiesel and diesel are being used increasingly worldwide because of environmental, economic, and social considerations.
Several countries use biodiesel blends with different blending limits. Therefore, it is necessary to develop or improve methods
to quantify the biodiesel level in a diesel/biodiesel blend, to ensure compliance with legislation. The optical technique
based on the absorption of light in the mid-infrared has been successful for this application. However, this method presents
some challenges that must be overcome. In this paper, we propose a novel method, based on fluorescence spectroscopy, to determine
the biodiesel content in the diesel/biodiesel blend, which allows in loco measurements by using portable systems. The results showed that this method is both practical and more sensitive than the
standard optical method. 相似文献
919.
Andrade LH Lima SM Novatski A Udo PT Astrath NG Medina AN Bento AC Baesso ML Guyot Y Boulon G 《Physical review letters》2008,100(2):027402
This Letter reports the formation of Ti3+ in OH- free aluminosilicate glass melted under vacuum condition, with a very long lifetime (170 micros) and broad emission band shifted towards the visible region. This lifetime value was attributed to the trapping of the excited electrons by the glass defects and detrapping by thermal energy, and it is 2 orders of magnitude higher than those published for Ti3+ doped materials. Our results suggest that this glass is a promising system to overcome the challenge of extending the spectral range of traditional tunable solid state lasers towards the visible region. 相似文献
920.
L. R. Calixto D. M. Lima R. S. Queiroz A. N. S. Rastelli V. S. Bagnato M. F. Andrade 《Laser Physics》2008,18(11):1365-1369
The purpose of this study was to evaluate the polymerization effectiveness of a composite resin (Z-250) utilizing microhardness testing. In total, 80 samples with thicknesses of 2 and 4 mm were made, which were photoactivated by a conventional halogen light-curing unit, and light-curing units based on LED. The samples were stored in water distilled for 24 h at 37°C. The Vickers microhardness was performed by the MMT-3 microhardness tester. The microhardness means obtained were as follows: G1, 72.88; G2, 69.35; G3, 67.66; G4, 69.71; G5, 70.95; G6, 75.19; G7, 72.96; and G8, 71.62. The data were submitted to an analysis of variance (ANOVA’s test), adopting a significance level of 5%. The results showed that, in general, there were no statistical differences between the halogen and LED light-curing units used with the same parameters. 相似文献