Digests or extracts?—Some interesting but conflicting results for three widely differing polluted sediment samples

Three sets of samples have been investigated in some detail. One set is from a river polluted by mine workings, containing substantial levels of Fe, Mn,Cu, Zn and Ni with traces of many other metals. The second set consists of typical estuarine sediments contaminated from a wide range of industrial sources, and the third set consists of oily drilling cuttings from the sea bottom in the vicinity of a North Sea oil production platform.These samples have been subjected to treatment 1) with EDTA at two different pH's (extracts) 2) with HNO₃/H₂O₂ 3) with HNO₃/HCl and 4) with HNO₃/HCl/HF (digests). EDTA recoveries, compared toaqua regia digests, are often very reproducible, not dependent on pH, and usually significantly low. Nitric/peroxide andaqua regia digests often give very close results suggesting that these are meaningful values indicating the maximum levels of polluting metals in the sediments. However, the triple acid digest with HF does sometimes give higher values (and reasonable agreement for CRM's such as MESS-1) but with poorer reproducibility.     

A DFT analysis of the vibrational spectra of nitrobenzene

Raman and FTIR, spectra of nitrobenzene, nb, and its isotopomers, nb-¹⁵N, nb-¹³C₆ and nb-d₅, were obtained and the fundamental vibrational modes assigned with the aid of a B3LYP/6-311+G** calculation, without the need for scaling of the force constants. The changes in vibrational coupling between the nitro and benzene groups upon certain isotopic substitutions are well modelled by the calculation, which is able to reproduce the isotopic shifts in frequencies for the nitro vibrations, as well as changes in IR intensities.     

Detection of DNA probes using Diels Alder cycloaddition and SERRS

A number of methods for detecting specific DNA sequences have been used to provide data for use in diagnosis of disease states and examination of gene expression. This study shows how the use of labelled oligonucleotides created by Diels Alder cycloaddition can be used as surface enhanced resonance Raman scattering (SERRS) active probes that provide easily identifiable signals at low concentrations in a mixture. The probes were produced by first tagging the oligonucleotides with a furan residue at the 5'-terminus to act as the diene. Three specifically designed benzotriazole azo maleimide dyes were then used as dienophiles to undergo cycloaddition with the furan modified oligonucleotide to generate SERRS active probes. These probes gave excellent SERRS signals from a silver-PVA film. Surface mapping of the silver PVA film indicated that the distribution of the dyes was uniform and that the number of moles of probe detected at any one time was approximately in the attomole region.     

Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the Au^I d¹⁰ metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of Au^I–Au^I interactions in 2 a , b .     

Metallocenes with Cp Ring-Fused to Chalcogen Heterocycles: Synthesis and Polymerization Results

Abstract

Substituted metallocene ligands containing cyclopentadiene ring fused to either selenophene or benzo[b]tellurophene were prepared following methods previously developed for analogs containing sulfur. 5-Methyl-4,5-dihydro-cyclopenta[b]-selenophen-6-one ( 2 ) and 3-Methyl-3,4-dihydro-benzo[b]cyclopenta[d]telluraphen-2-one ( 7 ) (major isomers) were prepared by polyphosphoric acid catalyzed Friedel-Crafts acylation/Nazarov cyclization of methacrylic acid onto selenophene and respectively benzo[b]tellurophene. Following reduction of the ketone to alcohol, then dehydration, the chalcogen-containing cyclopentadiene olefins were prepared. The olefins were deprotonated with n-butyllithium followed by either bridging with dichlorodimethylsilane, deprotonation and metallation, or deprotonation and direct metallation. In this manner, isomeric mixtures of –rac/-meso dimethylsilanediylbis(η⁵-5-Methyl-cyclopenta[b]selenophen-yl)zirconium dichloride ( 5 ) Bis(η^5?2-methyl-cyclopenta[b][1 Brintzinger, H. H., Fischer, D., Mülhaupt, R., Rieger, B. and Waymouth, R. 1995. Angew. Chem., 107: 1255[Crossref] , [Google Scholar]]benzotelluraphen-yl)zirconium dichloride ( 9 ) were prepared and characterized. Complexes formed active olefin polymerization catalyst when activated with methylalumoxane. Polymerization results with ethylene and propylene are included.     

Developments in microscale and nanoscale sensors for biomedical sensing

The widespread use of point of care testing in biomedical and clinical applications is a major aim of the electrochemical field. A large number of groups are working on lab-on-a-chip systems or sensor arrays which are underpinned by electrochemical detection methodologies. Miniaturized transducers have the potential to be adopted in such systems for diagnosis of a range of diseases in both clinical and nonclinical settings. In this review, we will present the current trends and state of the art for a selection of miniaturized sensing elements (microelectrodes, nanoelectrodes, and field-effect transistors) and provide an impression of current technologies, their associated performance characteristics, and also considering the major barriers to adoption and how they might be surmounted in future so these technologies can fulfil their early promise.     

Properties of polymer blends and triblock copolymers obtained by neutron scattering

Static and dynamic scattering properties of polymer blends and block copolymers are examined within the random phase approximation (RPA). A self-consistent theoretical scheme for a simultaneous analysis of elastic and quasielastic scattering data is presented. The case of a triblock copolymer made of an ordinary central block and two deuterated lateral blocks in a matrix of deuterated homopolymers is considered in detail. The theoretical predictions of the RPA are compared with the experimental data obtained by elastic neutron scattering experiments using mixtures of deuterated poly(dimethylsiloxane) homopolymers and copolymers made of three blocks of approximately equal sizes. The lateral blocks are deuterated poly(dimethylsiloxane) and the central one is an ordinary poly(dimethylsiloxane). A good agreement is found in the whole range of wavevectors covered by the experiments. An extension of the RPA to the analysis of the dynamical scattering data for the same systems is put forward. It is shown how the time relaxations of the bare response functions obtained from the single chain dynamics are used to extract the intermediate scattering function characterizing the system of interacting chains. © 1996 John Wiley & Sons, Inc.     

Self-assembled alkanethiol structures on gold: A further insight into the origins of structural rearrangement phenomena

Self-assembled structures of alkanethiols that have been deposited on gold from ethanolic solutions are susceptible to both chemical and physical changes: ethanol provides a medium for the formation of S-alkyl hydrogen thiocarbonates and related compounds via reaction with dissolved, atmospheric, CO₂. Deposition from ethanolic solutions results in multilayered structures incorporating these compounds, which at room temperature are susceptible to time-dependent structural rearrangement and molecular migration.     

Probing the independence of formant control using altered auditory feedback

Two auditory feedback perturbation experiments were conducted to examine the nature of control of the first two formants in vowels. In the first experiment, talkers heard their auditory feedback with either F1 or F2 shifted in frequency. Talkers altered production of the perturbed formant by changing its frequency in the opposite direction to the perturbation but did not produce a correlated alteration of the unperturbed formant. Thus, the motor control system is capable of fine-grained independent control of F1 and F2. In the second experiment, a large meta-analysis was conducted on data from talkers who received feedback where both F1 and F2 had been perturbed. A moderate correlation was found between individual compensations in F1 and F2 suggesting that the control of F1 and F2 is processed in a common manner at some level. While a wide range of individual compensation magnitudes were observed, no significant correlations were found between individuals' compensations and vowel space differences. Similarly, no significant correlations were found between individuals' compensations and variability in normal vowel production. Further, when receiving normal auditory feedback, most of the population exhibited no significant correlation between the natural variation in production of F1 and F2.