Merovingian ring-fort

One could argue that there are many approaches to site specifically as there are specific sites. Each site has a variety of influences such as visibility and natural and cultural histories. Human impositions that endure do so because of some canniness, some appreciation of how the current will live with the past.

Phenyl-ring disorder in the two-dimensional hydrogen-bonded structure of the 1:1 proton-transfer salt of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with L-tartaric acid

The structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenylazo)aniline], 4-(phenyldiazenyl)anilinium hydrogen 2R,3R-tartrate C12H12N3+ . C4H6O6- has been determined at 200 K. The asymmetric unit of the compound contains two independent phenylazoanilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of both cations have identical 50% rotational disorder. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxylic O--H...O~carboxyl~ hydrogen bonds [graph set C7] which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxyl O--H...O hydrogen-bonding links. The anilinium groups of the phenyldiazenyl cations are incorporated into the sheets and also provide internal hydrogen-bonding extensions while their aromatic tails layer in the structure without significant interaction except for weak \p--\p interactions [minimum ring centroid separation, 3.844(3) \%A]. The hydrogen L-tartrate residues of both anions have the common short intramolecular hydroxyl O--H...O~carboxyl~ hydogen bonds. This work has provided a solution to the unusual disorder problem inherent in the structure of this salt as well as giving another example of the utility of the hydrogen tartrate in the generation of sheet substructures in molecular assembly processes.

The strength and failure of silica optical fibers

The mechanical strength and failure behavior of conventional and microstructured silica optical fibers was investigated using a tensile test and fracture mechanics and numerical analyses. The effect of polymer coating on failure behavior was also studied. The results indicate that all these fibers fail in a brittle manner and failure normally starts from fiber surfaces. The failure loads observed in coated fibers are higher than those in bare fibers. The introduction of air holes reduces fiber strength and their geometrical arrangements have a remarkable effect on stress distribution in the longitudinal direction. These results are potentially useful for the design, fabrication and evaluation of optical fibers for a wide range of applications.

Living characteristics of the free-radical ring-closing polymerization of diallyldimethylammonium chloride

In this communication we provide the most recent results on RAFT-mediated ring-closing polymerization of diallyldimethylammonium chloride (DADMAC). The polymerization was carried out in aqueous solution employing 2,2′-azobis(2-methylpropionamidine)-dihydrochloride as the free radical initiator and trithiocarbonate RAFT agent (2-{[(dodecylsulfanyl)carbonothioyl sulfanyl]}propanoic acid, DoPAT) as the controlling RAFT agent. The results show that – while the system is not as completely controlled as previously described – it is nevertheless possible to mediate the polymerization of DADMAC and impart some living characteristics onto the system. The initial study on the RAFT-mediated polymerization of DADMAC may have overestimated the degree of livingness within this reaction. However, it is possible – at low conversions – for some living characteristics to be observed, as the evolution of molecular weight with conversion is linear. In addition, polymers with a reasonably narrow polydispersity can be isolated.

A novel method for the synthesis of monodisperse gold-coated silica nanoparticles

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN)2]?) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]? complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au0) proceeding by an inner sphere mechanism. The residual [Au(MeCN)2]? complex was allowed to react with water, disproportionating into Au0 and Au(III), respectively, with the Au0 adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au0 by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.