全文获取类型
收费全文 | 1000篇 |
免费 | 37篇 |
国内免费 | 2篇 |
专业分类
化学 | 691篇 |
晶体学 | 10篇 |
力学 | 31篇 |
数学 | 143篇 |
物理学 | 164篇 |
出版年
2023年 | 5篇 |
2022年 | 35篇 |
2021年 | 41篇 |
2020年 | 23篇 |
2019年 | 29篇 |
2018年 | 14篇 |
2017年 | 25篇 |
2016年 | 48篇 |
2015年 | 35篇 |
2014年 | 32篇 |
2013年 | 71篇 |
2012年 | 85篇 |
2011年 | 90篇 |
2010年 | 43篇 |
2009年 | 65篇 |
2008年 | 75篇 |
2007年 | 58篇 |
2006年 | 40篇 |
2005年 | 34篇 |
2004年 | 40篇 |
2003年 | 16篇 |
2002年 | 21篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1966年 | 1篇 |
1932年 | 1篇 |
1914年 | 1篇 |
1913年 | 1篇 |
1905年 | 1篇 |
1904年 | 1篇 |
1890年 | 1篇 |
排序方式: 共有1039条查询结果,搜索用时 31 毫秒
61.
Effect of viscosity of a liquid membrane containing oleyl alcohol on the pertraction of butyric acid
Marek Blahušiak Ján Marták Fernando Miranda Štefan Schlosser José A. Teixeira 《Chemical Papers》2013,67(12):1560-1568
Solvent formulation is important in the optimization of the mass-transfer through supported liquid membranes (SLM) in pertraction and membrane extraction. Oleyl alcohol (OA) is frequently used as the solvent or diluent in the extraction of carboxylic acids. A disadvantage of OA is its relatively high viscosity of 28.32 mPa s at 25°C. This can be decreased by the application of a less viscous OA diluent, e.g. dodecane. The relationship between the ratio of the distribution coefficient of butyric acid (BA), D F, and the viscosity of OA-dodecane solvents, µ, as extraction and transport characteristics, and the overall mass-transfer coefficient, K p, through SLMs was analyzed. Dependence of the D F/µ ratio on the OA concentration showed a maximum at the OA concentration of 15 mass % to 30 mass %. The OA concentration dependence of K p for SLMs exhibited also a maximum at about 30 mass % and 20 mass % of OA at the BA concentration driving force of 0.12 kmol m?3 and 0.3 kmol m?3, respectively. Shifting of the maximum in K p dependences towards lower OA concentrations by increasing the BA concentration driving force is in agreement with the D F/µ ratio dependence. Using pure OA as the solvent or diluent is not preferable and a mixture of a low viscosity diluent with the OA concentration below 40 mass % should be used. The presented results show the potential of the D F/µ ratio in the screening and formulation of solvents in extraction and SLM optimization. 相似文献
62.
Dr. Zijie Zhang Dr. Jiuxing Li Jimmy Gu Ryan Amini Hannah D. Stacey Jann C. Ang Dawn White Prof. Dr. Carlos D. M. Filipe Prof. Dr. Karen Mossman Prof. Dr. Matthew S. Miller Prof. Dr. Bruno J. Salena Prof. Dr. Deborah Yamamura Dr. Payel Sen Prof. Dr. Leyla Soleymani Prof. Dr. John D. Brennan Prof. Dr. Yingfu Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(15):e202200078
We report on a unique DNA aptamer, denoted MSA52, that displays universally high affinity for the spike proteins of wildtype SARS-CoV-2 as well as the Alpha, Beta, Gamma, Epsilon, Kappa, Delta and Omicron variants. Using an aptamer pool produced from round 13 of selection against the S1 domain of the wildtype spike protein, we carried out one-round SELEX experiments using five different trimeric spike proteins from variants, followed by high-throughput sequencing and sequence alignment analysis of aptamers that formed complexes with all proteins. A previously unidentified aptamer, MSA52, showed Kd values ranging from 2 to 10 nM for all variant spike proteins, and also bound similarly to variants not present in the reselection experiments. This aptamer also recognized pseudotyped lentiviruses (PL) expressing eight different spike proteins of SARS-CoV-2 with Kd values between 20 and 50 pM, and was integrated into a simple colorimetric assay for detection of multiple PL variants. This discovery provides evidence that aptamers can be generated with high affinity to multiple variants of a single protein, including emerging variants, making it well-suited for molecular recognition of rapidly evolving targets such as those found in SARS-CoV-2. 相似文献
63.
Arajo Joana C. Teixeira Pilar Fangueiro Raul Ferreira Diana P. 《Cellulose (London, England)》2022,29(10):5659-5676
Cellulose - Core–shell nanoparticles (NPs) based on metal oxides, namely magnesium oxide (MgO) and silica (SiO2), are a fantastic alternative for natural fibers’ functionalization. In... 相似文献
64.
Jaume Llibre Marco Antonio Teixeira Joan Torregrosa 《Mathematical Physics, Analysis and Geometry》2007,10(3):237-249
The goal of this paper is double. First, we illustrate a method for studying the bifurcation of limit cycles from the continuum
periodic orbits of a k-dimensional isochronous center contained in ℝ
n
with n ⩾ k, when we perturb it in a class of differential systems. The method is based in the averaging theory. Second, we consider a particular polynomial differential
system in the plane having a center and a non-rational first integral. Then we study the bifurcation of limit cycles from
the periodic orbits of this center when we perturb it in the class of all polynomial differential systems of a given degree.
As far as we know this is one of the first examples that this study can be made for a polynomial differential system having
a center and a non-rational first integral.
The first and third authors are partially supported by a MCYT/FEDER grant MTM2005-06098-C01, and by a CIRIT grant number 2005SGR-00550.
The second author is partially supported by a FAPESP–BRAZIL grant 10246-2. The first two authors are also supported by the
joint project CAPES–MECD grant HBP2003-0017. 相似文献
65.
Lucas J. M. F. Prezas P. R. Soreto Teixeira S. Ferreira N. M. Sales A. J. M. Melo B. M. G. Graça M. P. F. 《Journal of Sol-Gel Science and Technology》2021,98(3):580-592
Journal of Sol-Gel Science and Technology - Lithium ferrite (LiFe5O8) in the cubic crystal system is a very important and versatile material for several technological applications as it possesses... 相似文献
66.
Yaqin Xu Zhuyuan Zhang Dr. M. Monsur Ali Joanna Sauder Xudong Deng Karen Giang Sergio D. Aguirre Prof. Dr. Robert Pelton Prof. Dr. Yingfu Li Prof. Dr. Carlos D. M. Filipe 《Angewandte Chemie (International ed. in English)》2014,53(10):2620-2622
An odor‐based sensor system that exploits the metabolic enzyme tryptophanase (TPase) as the key component is reported. This enzyme is able to convert an odorless substrate like S‐methyl‐L ‐cysteine or L ‐tryptophan into the odorous products methyl mercaptan or indole. To make a biosensor, TPase was biotinylated so that it could be coupled with a molecular recognition element, such as an antibody, to develop an ELISA‐like assay. This method was used for the detection of an antibody present in nM concentrations by the human nose. TPase can also be combined with the enzyme pyridoxal kinase (PKase) for use in a coupled assay to detect adenosine 5′‐triphosphate (ATP). When ATP is present in the low μM concentration range, the coupled enzymatic system generates an odor that is easily detectable by the human nose. Biotinylated TPase can be combined with various biotin‐labeled molecular recognition elements, thereby enabling a broad range of applications for this odor‐based reporting system. 相似文献
67.
A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Henrique F. Carvalho Dr. João M. C. Teixeira Carlos T. B. Paula Prof. Petr Hermann Dr. Carlos Platas‐Iglesias Prof. Stephane Petoud Prof. Éva Tóth Prof. Carlos F. G. C. Geraldes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14834-14845
We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid= L1 ) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the GdIII complex may be sufficient for biological applications. A detailed structural study of the complexes by 1H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the 1H NMR paramagnetic shifts induced by YbIII. The water‐exchange rate of the GdIII complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$ =6.7×106 s?1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of LnIII ions emitting in both the visible (EuIII and TbIII) and NIR (PrIII, NdIII, HoIII, YbIII) spectral regions. The emission quantum yield determined for the YbIII complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$ =7.3(1)×10?3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI. 相似文献
68.
Synthesis of New Chlorin e6 Trimethyl and Protoporphyrin IX Dimethyl Ester Derivatives and Their Photophysical and Electrochemical Characterizations
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. José C. J. M. D. S. Menezes Prof. M. Amparo F. Faustino Prof. Kleber T. de Oliveira Dr. Marciana P. Uliana Prof. Vitor F. Ferreira Dr. Steffen Hackbarth Prof. Beate Röder Dr. Thiago Teixeira Tasso Dr. Taniyuki Furuyama Prof. Nagao Kobayashi Prof. Artur M. S. Silva Prof. M. Graça P. M. S. Neves Prof. José A. S. Cavaleiro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13644-13655
In view of increasing demands for efficient photosensitizers for photodynamic therapy (PDT), we herein report the synthesis and photophysical characterizations of new chlorin e6 trimethyl ester and protoporphyrin IX dimethyl ester dyads as free bases and ZnII complexes. The synthesis of these molecules linked at the β‐pyrrolic positions to pyrano[3,2‐c]coumarin, pyrano[3,2‐c]quinolinone, and pyrano[3,2‐c]naphthoquinone moieties was performed by using the domino Knoevenagel hetero Diels–Alder reaction. The α‐methylenechromanes, α‐methylenequinoline, and ortho‐quinone methides were generated in situ from a Knoevenagel reaction of 4‐hydroxycoumarin, 4‐hydroxy‐6‐methylcoumarin, 4‐hydroxy‐N‐methylquinolinone, and 2‐hydroxy‐1,4‐naphthoquinone, respectively, with paraformaldehyde in dioxane. All the dyads as free bases and as ZnII complexes were obtained in high yields. All new compounds were fully characterized by 1D and 2D NMR techniques, UV/Vis spectroscopy, and HRMS. Their photophysical properties were evaluated by measuring the fluorescence quantum yield, the singlet oxygen quantum yield by luminescence detection, and also the triplet lifetimes were correlated by flash photolysis and intersystem crossing (ISC) rates. The fluorescence lifetimes were measured by a time‐correlated single photon count (TCSPC) method, fluorescence decay associated spectra (FDAS), and anisotropy measurements. Magnetic circular dichroism (MCD) and circular dichroism (CD) spectra were recorded for one ZnII complex in order to obtain information, respectively, on the electronic and conformational states, and interpretation of these spectra was enhanced by molecular orbital (MO) calculations. Electrochemical studies of the ZnII complexes were also carried out to gain insights into their behavior for such applications. 相似文献
69.
Sana Jahanshahi‐Anbuhi Kevin Pennings Vincent Leung Dr. Meng Liu Carmen Carrasquilla Dr. Balamurali Kannan Prof. Dr. Yingfu Li Prof. Dr. Robert Pelton Prof. Dr. John D. Brennan Prof. Dr. Carlos D. M. Filipe 《Angewandte Chemie (International ed. in English)》2014,53(24):6155-6158
A simple and inexpensive method is reported for the long‐term stabilization of enzymes and other unstable reagents in premeasured quantities in water‐soluble tablets (cast, not compressed) made with pullulan, a nonionic polysaccharide that forms an oxygen impermeable solid upon drying. The pullulan tablets dissolve in aqueous solutions in seconds, thereby facilitating the easy execution of bioassays at remote sites with no need for special reagent handling and liquid pipetting. This approach is modular in nature, thus allowing the creation of individual tablets for enzymes and their substrates. Proof‐of‐principle demonstrations include a Taq polymerase tablet for DNA amplification through PCR and a pesticide assay kit consisting of separate tablets for acetylcholinesterase and its chromogenic substrate, indoxyl acetate, both of which are highly unstable. The encapsulated reagents remain stable at room temperature for months, thus enabling the room‐temperature shipping and storage of bioassay components. 相似文献
70.
Filipe Belarmino de Lima Gessenildo Pereira Rodrigues Juracy Regis de Lucena Júnior Elizete Ventura Rui Fausto Igor Reva Silmar Andrade do Monte 《International journal of quantum chemistry》2020,120(16):e26263
Multi-reference configuration interaction, MR-CI (including extensivity corrections, named +Q), calculations were performed on the S0–S3 states of cyclohexa-2,4-diene-1-thione (thione 24 ) and cyclohexa-2,5-diene-1-thione (thione 25 ), which are thione isomers of thiophenol. Several types of uncontracted MR-CIS and MR-CISD wavefunctions were employed, comprising MR-CI expansions as large as ~365 × 106 configuration state functions. The nature of the studied excited states was characterized. Vertical excitation energies (ΔE) and oscillator strengths (f) were computed. The most intense transitions (S0 → S2 for 24 and S0 → S3 for 25 ) did not change with the wavefunction, although a variation as large as ~1 eV was obtained for the S3 state of 24 , at the highest (MR-CI+Q) level. On the other hand, ΔE changed at most by ~0.56 eV for 25 as the wavefunction changes, at the same level. The S1 state of both thiones was found to have nπ* character and is in the visible region. For 24 , S2 and S3 are ππ* and nπ* states, respectively, while for 25 the reverse order is obtained. S2 and S3 are in the range ~3.5 to 5.2 eV, again at the highest level. It is the first time that the excited states of the title molecules are studied. The computed results agree with the experimental onset of photoreactions of thiones 24 and 25 found by Reva et al (Phys. Chem. Chem. Phys., 2015 , 17, 4888). 相似文献