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991.
Ana Isabel González Flórez Eike Mucha Dr. Doo‐Sik Ahn Sandy Gewinner Dr. Wieland Schöllkopf Prof. Dr. Kevin Pagel Dr. Gert von Helden 《Angewandte Chemie (International ed. in English)》2016,55(10):3295-3299
Here we present a combined experimental and theoretical study on the secondary structure of isolated proteins as a function of charge state. In infrared spectra of the proteins ubiquitin and cytochrome c, amide I (C=O stretch) and amide II (N–H bend) bands can be found at positions that are typical for condensed‐phase proteins. For high charge states a new band appears, substantially red‐shifted from the amide II band observed at lower charge states. The observations are interpreted in terms of Coulomb‐driven transitions in secondary structures from mostly helical to extended C5‐type hydrogen‐bonded structures. Support for this interpretation comes from simple energy considerations as well as from quantum chemical calculations on model peptides. This transition in secondary structure is most likely universal for isolated proteins that occur in mass spectrometric experiments. 相似文献
992.
Multi‐responses Methodology Applied in the Electroanalytical Determination of Hair Dye by Using Printed Carbon Electrode Modified with Graphene 下载免费PDF全文
Felipe Fantinato Hudari Sergio Luis Costa Ferreira Maria Valnice Boldrin Zanoni 《Electroanalysis》2016,28(5):1085-1092
This paper describes a rapid and sensitive method for determination of the hair dye Basic Blue 41 in wastewater samples using screen‐printed carbon electrodes modified with graphene (SPCE/Gr). The method is based on the reversible reduction of azo groups of the dye at potential of ?0.23 V/?0.26 V, where both the anodic and cathodic currents increased 1,300 % when compared to screen‐printed carbon (SPCE) and glassy carbon electrodes (GCE). The optimization of a square wave voltammetric method was performed by means of 23 factorial design, Doehlert matrix and multi‐response assays, and the best parameters were: frequency (54.8 Hz), step potential (6 mV), pulse amplitude (43.7 mV) and pH 4.5. The analytical curve was constructed from 3.00×10?8 to 2.01×10?6 mol L?1, with detection and quantification limits of 5.00×10?9 and 1.70×10?8 mol L?1, respectively. The repeatability of the method evaluated for 10 consecutive measurements at concentrations of 1.70×10?7 mol L?1 and 1.70×10?6 mol L?1, showed relative standard deviation of 3.56 and 0.57 %, respectively. The sensor based in SPCE/Gr was successfully applied in wastewater samples collected from a drinking water treatment plant and validated by comparison with HPLC‐DAD method with good accuracy. 相似文献
993.
Two Ru(II) complexes, [Ru(bpy)2L](ClO4)2 (1) and [Ru(bpy)2L'](BF4)2 (2), where bpy is 2,2'-bipyridine, L is diacetyl dihydrazone, and L' 1:2 is the condensate of L and acetone, are synthesized. From X-ray crystal structures, both are found to contain distorted octahedral RuN(6)(2+) cores. NMR spectra show that the cations in 1 and 2 possess a C2 axis in solution. They display the expected metal-to-ligand charge transfer (1MLCT) band in the 400-500 nm region. Complex 1 is nonemissive at room temperature in solution as well as at 80 K. In contrast, complex 2 gives rise to an appreciable emission upon excitation at 440 nm. The room-temperature emission is centered at 730 nm (lambda(em)(max)) with a quantum yield (Phi(em)) of 0.002 and a lifetime (tau(em)) of 42 ns in an air-equilibrated methanol-ethanol solution. At 80 K, Phi(em) = 0.007 and tau(em) = 178 ns, with a lambda(em)(max) of 690 nm, which is close to the 0-0 transition, indicating an 3MLCT excited-state energy of 1.80 eV. The radiative rate constant (5 x 10(4) s(-1)) at room temperature and 80 K is almost temperature independent. From spectroelectrochemistry, it is found that bpy is easiest to reduce in 2 and that L is easiest in 1. The implications of this are that in 2 the lowest (3)MLCT state is localized on a bpy ligand and in 1 it is localized on L. Transient absorption results also support these assignments. As a consequence, even though 2 shows a fairly strong and long-lived emission from a Ru(II) --> bpy CT state, the Ru(II) --> L CT state in 1 shows no detectable emission even at 80 K. 相似文献
994.
Luiz Pereira Ramos Helena Maria Wilhelm 《Applied biochemistry and biotechnology》2005,123(1-3):807-819
In recent years, the concept of producing biodiesel from renewable lipid sources has regained international attention. In
Brazil, a national program was launched in 2002 to evaluate the technical, economic, and environmental competitiveness of
biodiesel in relation to the commercially available diesel oil. Several research projects were initiated nationwide to investigate
and/or optimize biodiesel production from renewable lipid sources and ethanol derived from sugarcane (ethyl esters). Once
implemented, this program will not only decrease our dependence on petroleum derivatives but also create new market opportunities
for agribusiness, opening new jobs in the countryside, improving the sustainability of our energy matrix, and helping the
Brazilian government to support important actions against poverty. This article discusses the efforts to develop the Brazilian
biodiesel program in the context of technical specifications as well as potential oilseed sources. 相似文献
995.
Kinga Nawalany Aleksandra Rusin Mariusz Kpczyski Alexei Mikhailov Gabriela Kramer-Marek Mirosaw
nietura Jan Potowicz Zdzisaw Krawczyk Maria Nowakowska 《Journal of photochemistry and photobiology. B, Biology》2009,97(1):8-17
Two photosensitizing systems: (1) tetrakis(4-hydroxyphenyl)porphyrin (p-THPP) encapsulated in sterically stabilized liposomes (SSL) and (2) p-THPP functionalized by covalent attachment of poly(ethylene glycol) (p-THPP–PEG2000) were studied in vitro. The dark and photo cytotoxicity of these systems were evaluated on two cell lines: HCT 116, a human colorectal carcinoma cell line, and DU 145, a prostate cancer cell line and compared with these determined for free p-THPP. It was demonstrated that both encapsulation in liposomes as well as attachment of PEG chain result in pronounced reduction of the dark cytotoxicity of the parent porphyrin. The liposomal formulation showed higher than p-THPP–PEG2000 photocytotoxicity towards both cell lines used in the studies. 相似文献
996.
Saracino MA Mercolini L Musenga A Bugamelli F Raggi MA 《Journal of separation science》2008,31(10):1851-1859
Three analytical methods have been developed and compared for the quality control of a new formulation (Soymen GN(R) capsules) containing soy extract and melatonin for the treatment of menopausal symptoms. The first method is based on MEKC with diode-array detection, using a mixture of basic carbonate buffer (95%) and methanol (5%), containing 55 mM SDS, as the BGE. The second method is an HPLC method with UV detection at 260 nm. The third method is an HPLC method coupled to amperometric detection which is carried out at an oxidation potential of +0.8 V. In both HPLC systems, the chromatographic separation is obtained on an RP C18 column using a mixture of ACN and an acidic phosphate buffer (25:75 v/v) as the mobile phase. A feasible pretreatment procedure with a methanol/water mixture has been implemented to achieve the quantitative extraction of the main soy isoflavones and of melatonin from the capsules. The results obtained with the three methods are in good agreement with each other and satisfactory in terms of linearity (r(2) >0.9996), precision (RSD <5.4%) and accuracy (recovery >97%). Thus, each of the three analytical methods seems to be suitable for the simultaneous analysis of the main soy isoflavones and melatonin in the new commercial formulation. 相似文献
997.
Maria S. Tarasenko Nikolay G. Naumov Dmitry Yu. Naumov Sung-Jin Kim Vladimir E. Fedorov 《Polyhedron》2008
A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re6Te8(CN)6]3− was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H2O)4}{Re6Te8(CN)6}] · 2.5H2O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H2O)3}{Re6Te8(CN)6}] · 2.5H2O (2) and [{Yb(H2O)4}{Re6Te8(CN)6}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μB for compound 2 and 10.79 μB for compound 5 with weak antiferromagnetic ordering appeared at low temperatures. 相似文献
998.
Obtaining the total wavefunction evolution of interacting quantum systems provides access to important properties, such as entanglement, shedding light on fundamental aspects, e.g., quantum energetics and thermodynamics, and guiding towards possible application in the fields of quantum computation and communication. We consider a two-level atom (qubit) coupled to the continuum of travelling modes of a field confined in a one-dimensional chiral waveguide. Originally, we treated the light-matter ensemble as a closed, isolated system. We solve its dynamics using a collision model where individual temporal modes of the field locally interact with the qubit in a sequential fashion. This approach allows us to obtain the total wavefunction of the qubit-field system, at any time, when the field starts in a coherent or a single-photon state. Our method is general and can be applied to other initial field states. 相似文献
999.
Measurements have been carried out on furnished orchestra platforms in four concert halls in Italy in order to describe the sound field perceived by musicians. The heterogeneous nature of the orchestra suggested a procedure able to take into account the mutual hearing between instrumental sections. The measured parameters were the early, late and total support, the reverberation time, the early decay time and the clarity index. A part of the study has been devoted to the measurement uncertainty estimation. The source directivity and the small displacements of the microphone influence the early decay time to a great extent while the on-platform spatial variability affects both the early decay time and the clarity index. Per-section early support shows differences that render the overall spatial mean inappropriate to describe the stage as a whole. For the other parameters an overall mean platform value can instead be suitable, even though, for the case of clarity a more evident group variability is observed. The values of late support, reverberation time, early decay time and clarity index, proposed in literature as suitable measures of reverberance for musicians, are not all intercorrelated, indicating that not all these parameters can be associated to the same subjective impression. 相似文献
1000.
A longitudinal study of MR diffusion changes in normal appearing white matter of patients with early multiple sclerosis 总被引:12,自引:0,他引:12
Caramia F Pantano P Di Legge S Piattella MC Lenzi D Paolillo A Nucciarelli W Lenzi GL Bozzao L Pozzilli C 《Magnetic resonance imaging》2002,20(5):383-388
BACKGROUND AND PURPOSE: The stage at which normal appearing white matter (NAWM) abnormalities first appear in multiple sclerosis (MS) is not clear. The aim of our study was to monitor water diffusion changes over time in NAWM of patients with early MS.METHODS: Out of a consecutive series of patients enrolled in a MR study on clinically isolated syndrome (CIS), we selected 19 subjects who had completed a one year follow-up. The MR scans obtained at baseline and at 12 months were reviewed according to the new criteria on the diagnosis of MS. Lesion load on T2 and T1 weighted images and the trace of the apparent diffusion coefficient in NAWM were measured both at baseline and at 12 months in patients and in 12 healthy controls.RESULTS: In three patients the diagnosis of MS was done at baseline based on MR. Thirteen patients developed MS during the study and in three patients the diagnosis remained "possible MS." TADC in NAWM in patients was significantly higher than in controls at the 12 months' follow-up but not at baseline (controls mean tADC +/- sd = 0.745 +/- 0.02 mm(2)/sec x 10(-3); patients mean tADC(12) +/- sd = 0.767 +/- 0.02 mm(2)/sec x 10(-3); p < 0.02). TADC and T2 lesion load at 12 months were significantly correlated (p < 0.01). Patients exhibiting tADC(12) above a confidence interval had a significantly greater EDSS score at the same time period (EDSS(12) +/- sd = 1.9 +/- 0.5 and = 1.1 +/- 0.4 respectively; p < 0.01).CONCLUSIONS: This study suggests that diffusion MR cannot detect alterations in NAWM of patients with a CIS suggestive of MS. After one year, when most patients develop MS, diffusion MR abnormalities in NAWM become apparent. These abnormalities are correlated with T2 lesion load and may contribute to neurological impairment. 相似文献