首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Tris-chelated complexes of aluminum with α-isopropenyltropolonate and α-isopropyltropolonate ligands can be considered prototypical complexes for the study of internal rearrangements through prismatic transient structures. Such isomerization paths, known as Bailar and Ray-Dutt twists, have been suggested for these compounds on the basis of dynamic NMR study, but modern computational methodologies have never been applied to corroborate this finding. In this paper, we report a computational investigation about the internal isomerization processes of the mentioned complexes. Both the Bailar and Ray-Dutt twists have been found as possible reaction paths. The prismatic structures along each reaction path have been described as transition structures rather than intermediate and have been computationally characterized. A comparison between experimental and computational kinetic data has been performed.  相似文献   

2.
Summary A coating of silicone SE-54 on Chromosorb W has been converted to an analytically stable, immobilized stationary phase layer by cross-linking with an organic peroxide. Up to 10% by weight has been applied in this manner. Excellent high temperature qualities are exhibited, such as low bleeding and good base line stability, during typical analyses.Poly (2,6-dimethyl-p-phenylene oxide) has also been crosslinked as a surface coating on Chromosorb W with an organic peroxide. From 3 to 4% by weight has been immobilized in this way. The resultant packing material, following high temperature conditioning, has been examined for use as an adsorbent of trace substances, similar to the applications to which such adsorbents as Tenax GC have commonly been applied, e.g. trace analysis of air. It appears to exhibit satisfactory properties for this analytical purpose.  相似文献   

3.
The reduction of tertiary phosphine oxides (TPOs) and sulfides with diisobutylaluminum hydride (DIBAL-H) has been studied in detail. An extensive solvent screen has revealed that hindered aliphatic ethers, such as MTBE, are optimum for this reaction at ambient temperature. Many TPOs undergo considerable reduction at ambient temperature and then stall due to inhibition. 31P and 13C NMR studies using isotopically labeled substrates as well as competition studies have revealed that the source of this inhibition is tetraisobutyldialuminoxane (TIBAO), which builds up as the reaction proceeds. TIBAO selectively coordinates the TPO starting material, preventing further reduction. Several strategies have been found to circumvent this inhibition and obtain full conversion with this extremely inexpensive reducing agent for the first time. Practical reduction protocols for these critical targets have been developed.  相似文献   

4.
A library of 32 organoruthenium compounds has been synthesised. Known and novel C-N cyclometalated compounds as well as N-C-N and N-N-C pincer derivatives of this metal have been used in this purpose. Most of the compounds have been tested for their in vitro antitumoral behaviours, good to excellent activities have thus been found. Several of the newly synthesized compounds pass the symbolic barrier of the nanomolar range for their IC(50) indicating a critical improvement. The level of activity is tentatively correlated to physicochemical properties of the compounds such as their Ru(III/II) redox potential and their lipophilicity (log P).  相似文献   

5.
Molecular imprinting technology has been employed for the first time to prepare a specifically affinity chromatographic stationary phase for speciation purposes. Tributyltin has been chosen as the template molecule and the non-covalent approach has been applied. Three different polymerization methods have been evaluated: (i) a composite material, (ii) a polymer prepared via-Iniferter grafting; (iii) an emulsion polymer. Columns packed with different polymers have been evaluated by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The chromatographic conditions as well as the analytical characteristics of the developed method are discussed in this paper. Our findings have shown formation of specific cavities in the grafted Iniferter as well as in the emulsion polymers with the latter achieving resolution of four organotin compounds. Detection limits are similar to those obtained with commercial, but not specific, stationary phases (6 pg for monobutyltin, MBT; 10 pg for both tributyltin, TBT, and triphenyltin, TPhT; and 20 pg for dibutyltin, DBT). The main advantage of this proposed stationary phase is that good recovery is obtained for all species, including MBT. Baseline resolution for TBT and TPhT has also been obtained. The high selectivity of this column prevents matrix interferences. The method has been validated by analyzing two biota reference materials (ERM-CE477 mussel tissue and T-38 oyster tissue).  相似文献   

6.
Yessotoxins (YTXs) are a group of polyether toxins which have been previously reported as responsible for seafood contamination in several places worldwide. Despite their toxicity, which is not yet fully discussed, YTXs have been reported as an interference in the success of mouse bioassay for the determination of diarrhetic shellfish poisoning (DSP) toxins, and therefore, efficient and reliable analytical methodologies are required to evaluate their presence, avoiding false positives for DSP. High-performance capillary electrophoresis (HPCE) is presented in this work as an alternative to HPLC technique widely used for the analysis of YTXs. Improvements in the applicability of HPCE have been carried out through the development of different CE modes as well as different detection modes. With this aim, micellar electrokinetic chromatography (MEKC) has been considered for an increased selectivity while an increased sensitivity was achieved by using sample stacking. Moreover, the coupling of CE with mass spectrometry allowed the confirmation of YTXs present in the contaminated samples evaluated in this work. The results obtained showed the potential of CE as an alternative to HPLC for the analysis of YTXs present in naturally contaminated samples.  相似文献   

7.
Recently developed MOF surface-coating techniques, the controlled SBU approach (CSA) for the generation of MOF-5, and the use of self-assembled monolayers have been combined to generate a wall-bonded, crosslinked stationary phase for gas chromatographic capillary columns displaying excellent performance in the separation of natural gas components. The chromatographic performance of this new type of column has been compared to the state-of-the-art solution for this separation problem, namely a coated silica column of the porous layer open tubular (PLOT) type. Chromatographic parameters such as separation, resolution, and tailing factors, as well as plate numbers and heights in the case of isothermal operation, have been determined. Kinetic and thermodynamic parameters characterizing the analyte-stationary phase interaction have been determined for various C1-C4 analytes.  相似文献   

8.
The environmental CRMs currently available from NRC Ottawa comprise four natural waters for trace elements, four biological tissues for trace elements and methylmercury, three marine sediments for major and trace elements (one sediment has certified values for butyltins) and one fish tissue for organochlorines (PCBs, dioxins). Although significant effort has been expended to maintain this suite of materials, several new initiatives have also recently been completed or are in progress. The certified value for arsenobetaine in Dogfish Muscle CRM DORM-2 has been established. The certification approaches, as well as the studies to determine extraction efficiency of this organoarsenic compound, are presented. A stability study has been completed for Hg in a natural water sample and plans are underway for production of a CRM. Assessment of micronutrient stability in seawater for the purposes of CRM production is continuing and progress on this initiative is discussed.  相似文献   

9.
The environmental CRMs currently available from NRC Ottawa comprise four natural waters for trace elements, four biological tissues for trace elements and methylmercury, three marine sediments for major and trace elements (one sediment has certified values for butyltins) and one fish tissue for organochlorines (PCBs, dioxins). Although significant effort has been expended to maintain this suite of materials, several new initiatives have also recently been completed or are in progress. The certified value for arsenobetaine in Dogfish Muscle CRM DORM-2 has been established. The certification approaches, as well as the studies to determine extraction efficiency of this organoarsenic compound, are presented. A stability study has been completed for Hg in a natural water sample and plans are underway for production of a CRM. Assessment of micronutrient stability in seawater for the purposes of CRM production is continuing and progress on this initiative is discussed.  相似文献   

10.
The aim of this work is basically centred in the improvement of the obtention of the peroxides precursors of macrocyclic lactones (C11 and C16) through the Story synthesis useful as raw materials for high performance linear polyesters. As a starting point, the yield has been increased respect to the classic synthesis using mild and intrinsically safer reactants. Concretely, a yield of 55% in triperoxide of cyclohexanone has been achieved using 35% hydrogen peroxide and phosphotungstic acid as catalyser. For this intention two factorial experimental designs, fractional and complete, have been carried out. The analytical method adequate for the reactive system studied (HPLC-UV-RI) has been chosen as well as the optimal operating conditions. A quantification of the risk on the first part of the reaction in calorimetric terms has been performed. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

11.
The problem of spectrochemical analysis of elements in solutions has been investigated for a number of elements across the periodic table using radioisotope-induced energy dispersive X-ray fluorescence method. In this study a low intensity109Cd X-ray source was used for characteristic X-ray excitation. Experimental parameters such as saturation thickness and critical thickness have been studied to evaluate their role in this method. Minimum detection limits, sensitivities and the nature of concentration calibration at critical thickness have been obtained as a function of Z to find the limits of the method. Results obtained have been discussed in the light of theories and potential areas of applicability of the method have been indicated.  相似文献   

12.
A new 10- and 12-membered ring zeolite, named ITQ-24, has been synthesized, and its structure has been solved. It has been found that this zeolite structure is topologically identical to that proposed for the hypothetical polymorph C of the SSZ-33/SSZ-26/CIT-1 family. This new zeolite has been achieved by using a rational approach of introducing Ge in the framework that has a directing effect toward zeolite structures with double-four-membered rings as secondary building units. Notoriously, active catalytic centers, such as Ti and Al, have been incorporated into this new zeolite, demonstrating that it is catalytically active for alkylation of aromatics.  相似文献   

13.
The complex of the reagent 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) with Bi(III) has been studied. The composition and stability of this complex have been determined. An analytical method for the spectrophotometric determination of Bi(III) using its complex with 5-Br-PADAP has been developed. Variables influencing the method such as pH, wavelength, and time have been studied. The limitations of this method and the effect of interfering ions have been investigated. Comparison of this method with other methods cited in the literature for the determination of Bi(III) is also included.  相似文献   

14.
Silanediols have been shown to be effective bioisosteres for the hydrated carbonyl group. Current methods for the formation of silanediols place a number of constraints on how and where this functionality may be used. A range of arylsilanes that would allow both the formation of arylsilanediols and that are also compatible with multi-step synthetic routes, have been investigated as possible precursors to silanediols. Through this study bis(2-furyl)silanes and, in particular, bis(2-thienyl)silanes have been identified as practical precursors to arylsilanediols.  相似文献   

15.
Since the discovery of graphene in the early 2000′s, polycyclic aromatic hydrocarbons (PAHs) have been resurrected and new synthetic tools have been developed to prepare unprecedented structures with unique properties. One application that has been overlooked for this class of molecules is organic solar cells (OSCs). In this account, we present the recent development in the preparation of moderate to low band gap PAHs that could potentially be used as semiconducting materials in OSCs. Our focus is directed toward all‐carbon PAHs as well as their polymeric analogs.  相似文献   

16.
Effects of microsolvating CH(5)(+) with up to four H(2) molecules have been investigated in terms of structures and energies. For the smaller complexes, benchmark calculations have been carried out using MP2 and CCSD(T) with basis sets up to aug-cc-pV5Z quality and energies have been extrapolated to the infinite basis set limit. It is found that MP2 calculations using the aug-cc-pVQZ basis set or better yield robust reference data for both structures and energies. More than 30 stationary points including minima and first-order as well as second-order stationary points have been characterized by this method and are discussed in terms of solvation motifs. Finally, the performance of several density functionals has been assessed for this very demanding case. Popular GGA functionals such as BLYP and PBE fail, whereas the TPSS meta-GGA functional captures many structural and energetic aspects of microsolvation satisfactorily.  相似文献   

17.
In this account, the synthesis and applications of pyrene‐fused acenes, as well as pyrene‐fused azaacenes, have been carefully reviewed. Moreover, the synthetic methods involving two key synthons (different lengths of dienes and ynes) have been included. Furthermore, the “clean reaction” strategy has been introduced for the preparation of pyrene‐fused acenes with a single terminal‐pyrene unit from tetracene to octacene, as well as for the synthesis of pyrene‐fused octatwistacenes and nonatwistacenes with double terminal‐pyrene units. Similarly, the synthons and the synthetic methods for pyrene‐fused azaacenes have also been summarized. The applications of pyrene‐fused acenes and pyrene‐fused azaacenes have been included.  相似文献   

18.
Sample preparation is an important issue in analytical chemistry, and is often a bottleneck in chemical analysis. So, the major incentive for the recent research has been to attain faster, simpler, less expensive, and more environmentally friendly sample preparation methods. The use of auxiliary energies, such as heat, ultrasound, and microwave, is one of the strategies that have been employed in sample preparation to reach the above purposes. Application of electrical driving force is the current state-of-the-art, which presents new possibilities for simplifying and shortening the sample preparation process as well as enhancing its selectivity. The electrical driving force has scarcely been utilized in comparison with other auxiliary energies. In this review, the different roles of electrical driving force (as a powerful auxiliary energy) in various extraction techniques, including liquid-, solid-, and membrane-based methods, have been taken into consideration. Also, the references have been made available, relevant to the developments in separation techniques and Lab-on-a-Chip (LOC) systems. All aspects of electrical driving force in extraction and separation methods are too specific to be treated in this contribution. However, the main aim of this review is to provide a brief knowledge about the different fields of analytical chemistry, with an emphasis on the latest efforts put into the electrically assisted membrane-based sample preparation systems. The advantages and disadvantages of these approaches as well as the new achievements in these areas have been discussed, which might be helpful for further progress in the future.  相似文献   

19.
新型固体参比电极的研制   总被引:4,自引:1,他引:4  
黄超伦  任聚杰 《分析化学》1996,24(7):816-819
  相似文献   

20.
Functionalization of saturated fluorocarbons with and without light   总被引:1,自引:0,他引:1  
Photochemical transformation of saturated fluorocarbons into tetrabutylammonium enolates has been improved, and a method employing ketyls as reductants has been developed that accomplishes the same chemistry without light. Enolates have been isolated as enol methyl ethers, from which they can be efficiently regenerated with tetrabutylammonium iodide. In other cases, enolates have been isolated as the corresponding ketone or stable enol. Fluorocarbon LUMO energies correlate with their reactivity and serve as a guide to the choice of ketyl. Use of this chemistry for fluoropolymer surface modification is discussed.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号