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61.
金属纳米颗粒,特别是金和它的双金属纳米颗粒作为强大的绿色催化剂广泛用于有机合成反应中。在一个反应体系中使用2个不同催化剂(如协同催化),在均相催化中是一个很好的策略。然而,这种方法仍在发展中。最近我们发现,金/钯双金属纳米颗粒与路易斯酸的协同催化体系可用于伯胺的N-烷基化:即酰胺与醇之间的氢自转移反应。我们详细报道了路易斯酸对该氢自转移反应的影响。结果表明,所选的路易斯酸不仅影响生成目标产物的反应路径,而且影响生成多个中间体和副产物的反应路径。弱的路易斯酸,如三氟甲磺酸碱土金属盐,非常适合酰胺的N-烷基化反应。 相似文献
62.
Paulius Kaškonas Žydrūmas Stanius Vilma Kaškonienė Kęstutis Obelevičius Ona Ragažinskineė Antanas žilinskas Audrius Maruška 《Chemical Papers》2016,70(12):1568-1577
This study describes the analysis of total hops essential oils from 18 cultivated varieties of hops, five of which were bred in Lithuania, and 7 wild hop forms using gas chromatography-mass spectrometry. The study sought to organise the samples of hops into clusters, according to 72 semi-volatile compounds, by applying a well-known method, k-means clustering analysis and to identify the origin of the Lithuanian hop varieties. The bouquet of the hops essential oil was composed of various esters, terpenes, hydrocarbons and ketones. Monoterpenes (mainly β-myrcene), sesquiterpenes (dominated by β-caryophyllene and α-humulene) and oxygenated sesquiterpenes (mainly caryophyllene oxide and humulene epoxide II) were the main compound groups detected in the samples tested. The above compounds, together with a-muurolene, were the only compounds found in all the samples. Qualitative and quantitative differences were observed in the composition of the essential oils of the hop varieties analysed. For successful and statistically significant clustering of the data obtained, expertise and skills in employing chemometric analysis methods are necessary. The result is also highly dependent on the set of samples (representativeness) used for segmentation into groups, the technique for pre-processing the data, the method selected for partitioning the samples according to the similarity measures chosen, etc. To achieve a large and representative data set for clustering analysis from a small number of measurements, numerical simulation was applied using the Monte Carlo method with normal and uniform distributions and several relative standard deviation values. The grouping was performed using the k-means clustering method, employing several optimal number of clusters evaluation techniques (Davies-Bouldin index, distortion function, etc.) and different data pre-processing approaches. The hop samples analysed were separated into 3 and 5 clusters according to the data filtering scenario used. However, the targeted Lithuanian hop varieties were clustered identically in both cases and fell into the same group together with other cultivated hop varieties from Ukraine and Poland. 相似文献
63.
64.
Artūrs Škute Sergejs Osipovs Davids Vardanjans 《International journal of environmental analytical chemistry》2016,96(1):1-14
Nitrogen isotope ratio of nitrate provides a powerful tool to investigate nitrate sources and cycling mechanisms. Although the use of an isotope ratio method for 15N/14N allows identifying the nitrate sources in rivers by estimating a seasonal variation of N-NO3 concentration, however, there are some restrictions. Nitrification, the conversion of NH4+ to NO3-, can proceed with significant nitrogen isotope fractionation, preferentially accumulating 14N in the produced NO3-, and can make it difficult to identify the nitrate source with a high proportion of the isotope δ15N. However, the uptake and assimilation of NH4+ and NO3- have the capability of affecting isotopic compositions of riverine nitrogen compounds, and this may hinder the determination of whether the impact of the nitrate source with a high proportion of the isotope δ15N reduces. In addition, this study demonstrates that nitrate nitrogen concentration may correlate with δ15NNO3 values both positively and negatively. Such correlations are the result of isotope effects during nitrogen transformation processes (e.g. nitrification and assimilation) and isotopic variability in the various nitrate sources. A comparison of NO3- concentration and δ15NNO3 can be used to further distinguish mixing from biological processing. However, in order to get a more precise answer regarding the nitrate sources, it would be useful to take both the data of nitrogen isotopes and data of oxygen isotopes present in nitrates. 相似文献
65.
M. Katkevičs A. Kontijevskis I. Mutule E. Sūna 《Chemistry of Heterocyclic Compounds》2007,43(2):151-159
A 30-membered library of coumarins has been synthesized in a microwave-assisted Pechmann reaction using neat trifluoroacetic
acid both as an acidic reagent and a reaction medium. Alternatively, polymer-supported sulfonic acid Amberlyst-15 could also
be employed to facilitate the formation of coumarins. The use of a specially-built microwave synthesizer with liquid handling
tools rendered the automated synthesis of a coumarin library feasible.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 200–208, February, 2007. 相似文献
66.
S. Stupnikova E. Petushkova D. Muceniece V. Lūsis 《Chemistry of Heterocyclic Compounds》2007,43(1):41-49
The recyclization of 1,4-dihydropyridines in aqueous-alcoholic hydrochloric acid medium proceeds with cleavage of a C-N bond
and pyridine ring opening. Cyclohexenone derivatives are formed as a result of the subsequent intramolecular crotonic condensation
of the acyclic intermediate. The leaving carbonyl substituents depart simultaneously with recyclization, depending on the
acidity of the reaction medium.
Dedicated to Prof. Dr. E. Lukevics on the occasion of his 70th birthday.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 49–58, January, 2007. 相似文献
67.
Žydrė Šaltienė Natalija Jatulienė Mudis Šalkauskas Daiva Brukštienė Asta Ruzgytė Aušra Tarasevičiūtė Julius Kalibatas 《Accreditation and quality assurance》2005,10(8):444-451
The estimation scheme of uncertainty of determination of 1-hydroxypyrene (1-OHP) in urine was developed analysing the main
stages of the analytical procedure: (1) preparation of 1-OHP standards, (2) creation of the calibration curve for the high
performance liquid chromatography (HPLC) analysis method with the evaluation of recovery, (3) measuring procedure of aliquot
of urine, (4) adjusting the pH of aliquot and hydrolysis with enzyme, (5) solid phase extraction, (6) concentration of the
extract, (7) injection of the extract to chromatograph and analysing by the HPLC method, (8) calculation of 1-OHP mass from
the calibration curve, (9) calculation of 1-OHP concentration in urine. The evaluation of the uncertainty is based on quantification
of individual components. Combined uncertainty was calculated using the law of propagation of uncertainties according to the
EURACHEM/CITAC guidelines. Level dependence of the uncertainty arises from the calibration curve.
The limits of detection and quantification were found to be equal to 0.03 and 0.1 ng/mL, respectively. The calculated expanded
level-dependent uncertainty covers 47–27–25% within the concentration range 0.03–0.1–0.4 ng/mL with the materials and equipment
used. These parameters could easily be recalculated according to the proposed scheme if there are some changes in the analysis
procedure. 相似文献
68.
Saulis G Lape R Praneviciūte R Mickevicius D 《Bioelectrochemistry (Amsterdam, Netherlands)》2005,67(1):101-108
The change of the pH of a NaCl solution (139-149 mM NaCl) buffered with 5-15 mM sodium phosphates (pH 7.4) during electromanipulation was studied. It has been determined that an increase in the pH value of electroporation solution of a whole chamber volume, caused by the application of electric field pulses, commonly used in cell electromanipulation procedures, can exceed 1-2 pH units. Several materials for the cathode were tested. In all cases a stainless steel anode was utilized. The aluminum cathode gave a two-fold greater DeltapH in comparison with platinum, copper or stainless steel cathodes. In addition, a substantial release of aluminum (up to 1 mg/l) from the cathode was observed. It has also been found that the shift in pH depended on the medium conductivity: DeltapH of the solution, in which sucrose was substituted for NaCl, was about 5 times less. On the basis of the results obtained here, to avoid the plausible undesirable consequences of the cathodic electrolysis processes, in particular under the conditions of strong electric treatment, it could be recommended that chambers with aluminum electrodes not be utilized and one should use strongly buffered solutions of low conductivity and alternating current (sine or square wave) bipolar electric pulses. 相似文献
69.
A simple and fast micellar electrokinetic chromatographic (MEKC) method for the determination of five main compounds (hydroquinone, metol, phenidone, 2-hydroxy-5-methylaminobenzenesulphonate and 2,5-dihydroxybenzenesulphonate) in X-ray film developing solutions was developed. The optimal conditions for the separation were established by varying the concentration of sodium dodecyl sulfate (SDS), the electrolyte pH and the temperature. Successful results were obtained with a 25mmolL–1 Tris-phosphate buffer at pH 9.0 in the presence of 50mmolL–1 SDS using direct UV detection at 214nm. Under these conditions, baseline separation of the five compounds was achieved in less than 8min. The method was validated in terms of precision, linearity, accuracy, and successfully applied to the analysis of X-ray film developing baths. 相似文献
70.
Changes of the radioactive decay rate of71Ge (T 1/2=11.43 days) have been studied experimentally for71Ge in some compounds of bivalent and quadrivalent germanium. Relative changes Δλ/λ of the electron capture probability have been measured, and the chemical changes Δρ(0) of the electron density at the germanium nuclei have been determined from these measurements. Values for the Mössbauer isomer shift calibration constants for the 67 keV γ-transition of73Ge have been estimated:C=δ/Δρ(0)=(0.061±0.020) mm·s?1/a.u., Δ〈r 2〉=(21±7)·10?3 fm2, ΔR/R=(6.9±2.3)·10?4. 相似文献