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21.
During 1998 and early 1999, shellfish samples from sites in Scotland were found to contain the amnesic shellfish poisoning toxin, domoic acid (DA). Two different techniques, liquid chromatography (LC) with UV diode-array detection and LC with mass spectrometric (MS) detection, were used to detect and confirm DA in shellfish extracts. The LC/UV method was validated for routine monitoring by recovery experiments on spiked mussel and scallop tissues with a certified mussel tissue used as reference material. Crude extracts of selected samples as well as extracts cleaned with strong anion exchange (SAX) were analyzed by both LC/UV and LC/MS. Good correlation (linear regression r2 = 0.996, slope = 0.93) between the 2 methods was found for cleaned extracts. Analyses of crude extracts by LC/UV produced false-positive results in 2 crab samples, whereas LC/MS analyses gave accurate results. It was concluded that LC/UV is a valid approach for routine monitoring of DA in shellfish when cleanup is performed with a SAX cartridge to prevent false positives. A variety of shellfish species were surveyed for DA content, including Pecten maximus (king scallops), Chlamys opercularis (queen scallop), Mytilus edulis (blue mussels), Cancer pugaris (crab), and Ensis ensis (razor fish). The highest concentration of DA was 105 microg/g in Pecten maximus.  相似文献   
22.
One possible route to the elusive biaxial nematic phase is through rod-disc dimers in which the rod and disc mesogenic units are linked via a flexible spacer. We have developed a continuous generic model of such rod-disc dimers in which neighbouring like groups tend to align parallel to each other while unlike groups tend to be orthogonal. A torsional potential controls the relative orientations of the groups within a single dimer; depending on the strength of the torsional potential, the groups may be orthogonal or parallel in the conformational ground state. Monte Carlo simulations show that a rigid rod-disc dimer is most likely to form a biaxial nematic phase if the anisotropies of the two groups are the same. Introduction of flexibility is found to have little effect on the qualitative behaviour of the dimer as the relative anisotropy of the two mesogenic groups is changed. However, when the torsional potential strongly favours the alignment of the rod and disc within a single molecule with their symmetry axes parallel there is a dramatic change. The system then exhibits a strong hysteresis in the molecular shape and biaxiality and the biaxial nematic-isotropic transition becomes strongly first order, in marked contrast to the second-order character usually found for this transition. This first-order transition is observed to occur for a range of relative anisotropies of the two groups rather than at a single point.  相似文献   
23.
The adsorption of linear, branched, and cyclic hydrocarbons in MCM-41 is studied using Configurational Bias Monte Carlo simulations. A new computational model for MCM-41 is proposed which, although simple, is able to predict adsorption isotherms which are in agreement with the scarce experimental data. The structure of the adsorbed phase is analyzed and found to be similar to that of studies using small, hard spheres trapped in pores. The adsorption of mixtures is investigated, and the adsorption hierarchy is discussed. The structure of the adsorbed mixture is revealed and shows that all components of the mixture exhibit structure, even if they are only adsorbed in small quantities. Finally, the model is modified to include surface roughness and the effect on the adsorption isotherms and structure of the adsorbed phase is discussed.  相似文献   
24.
Rapid, selective collision-dependent excitation of N2O following pumping of SF6 with a CO2 laser is reported. The N2O fluorescence rise depends on the pressure of each component and is dominated by the SF6-dependent contribution of 2290 ms?1 Torr?1. The subsequent fall is governed by V→V processes among SF6 vibrational modes.  相似文献   
25.
The utility of pentafluorophenyl esters for the selective introduction of functional units and branch points in well-defined poly(acrylic acid) (PAA) derivatives is demonstrated using a combination of controlled radical polymerization and postpolymerization modification. Reversible addition-fragmentation chain transfer enables the synthesis of well-defined copolymers—poly(pentafluorophenyl acrylate-co-tert-butyl acrylate)—with the active ester repeat units serving as attachment points for reaction with primary amines, specifically tris(2-(t-butoxycarbonyl)ethyl)methyl amine (Behera's amine). Deprotection using trifluoroacetic acid removes both the backbone and side chain t-butyl esters to give a series of branched PAA derivatives containing novel tricarboxylic acid side chains that are well suited to complexation and multidentate interactions. Surprisingly, the active ester homopolymer is shown to have the highest reactivity with Behera's amine when compared to copolymers with lower incorporation of pentafluorophenyl esters, suggesting an intriguing interplay of neighboring group effects and steric interactions. The ability to tune the efficiency of postpolymerization modification gives a library of PAA derivatives.  相似文献   
26.
本研究组在前期研究中发现, 改变溶剂的挥发速率可以调节体系中PE结晶和PVCH玻璃化之间的竞争, 进而调节PE结晶的受限程度. 超临界二氧化碳(scCO2)是一种非极性溶剂, 其对无定形聚合物(如PS)有很强的溶胀作用, 可显著降低聚合物的玻璃化转变温度, 提高原来被冻结的高分子链的活动能力. PVCH的分子结构与PS相似, 研究结果表明, scCO2对PVCH组分也有很强的溶胀能力, 导致PVCH的玻璃化转变温度降低, 从而可以改变PE嵌段的受限状态. 本文研究了PVCH-PE-PVCH在scCO2中的熔融再结晶行为.  相似文献   
27.
Electromotive-force measurements of cells without transference were used to determine the dissociation constant of the protonated form of the weak base 2-amino-2-methyl-1, 3-propanediol (Bis) in synthetic seawaters corresponding to salinities of 20, 35, and 45. Hydrogen electrodes and silver-silver chloride electrodes were used, together with standard potentials determined in an earlier investigation. The pK increases in linear fashion with the salinity (S) of the medium, for values of S from 0 to 45. The solvent effect is given by 8.802+0.00378S at 25°C with a mean deviation of 0.001. The medium effect of seawater on H° at 25°C is less than 200 cal-mol–1 and less than 0.2 cal-oK-mol–1 on S°.  相似文献   
28.
CO(2) capture by a task-specific ionic liquid   总被引:20,自引:0,他引:20  
Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function.  相似文献   
29.
A plot of the measured electron—ion recombination coefficient against the number density of ambient ammonia shows an unexpectedly early fall which, it is suggested, may be due to the collisional coupling between the dissociative states and the other states being weakened by the growth in the clustering.  相似文献   
30.
MoN and MoO molecules produced in a hollow cathode discharge have been trapped in Ne, Ar, and Kr matrices at 4.2 and 13 K and investigated by optical spectroscopy. Bands attributed to MoN were identified in the red and blue spectral regions and assigned by comparison with gas phase results to the A4πX4Σ? (a) and B4Σ → X4Σ? (a) transitions, respectively. The ground state of Mo14N has been identified as 4Σ? with ωe = 1040 cm?1 in an Ar matrix. Absorptions assigned to MoO in the red spectral region form the (0-0) and (1-0) bands of at least one electronic transition, but could not definitely be correlated with the gas phase results. The ground state vibrational frequency for Mo16O in an Ar matrix is 893.5 cm?1. Additionally, Mo2 absorptions centered at 19 305 cm?1 were shown to be part of a vibrational progression with an average spacing of 181 cm?1.  相似文献   
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