The critical role of water in spider silk and its consequence for protein mechanics

Due to its remarkable mechanical and biological properties, there is considerable interest in understanding, and replicating, spider silk's stress-processing mechanisms and structure-function relationships. Here, we investigate the role of water in the nanoscale mechanics of the different regions in the spider silk fibre, and their relative contributions to stress processing. We propose that the inner core region, rich in spidroin II, retains water due to its inherent disorder, thereby providing a mechanism to dissipate energy as it breaks a sacrificial amide-water bond and gains order under strain, forming a stronger amide-amide bond. The spidroin I-rich outer core is more ordered under ambient conditions and is inherently stiffer and stronger, yet does not on its own provide high toughness. The markedly different interactions of the two proteins with water, and their distribution across the fibre, produce a stiffness differential and provide a balance between stiffness, strength and toughness under ambient conditions. Under wet conditions, this balance is destroyed as the stiff outer core material reverts to the behaviour of the inner core.     

Evaluation of thermodynamic theories to predict interfacial tension between polystyrene and polypropylene melts

The commonly used thermodynamic theories (mean field theory and the square gradient theory) to predict interfacial tension between polymers have been modified. The results of these theoretical developments have not yet been fully tested and compared to experimental data. In this paper, experimental data for the effects of temperature, molecular weight, and molecular weight dispersity on interfacial tension for polypropylene/polystyrene polymer pairs are compared with the predictions of the new versions of the above theories. To evaluate these theories, it is necessary to know the Flory-Huggins interaction parameter for the polymer pairs studied. The relation correlating the Flory-Huggins interaction parameter to the Hildebrand solubility parameter was not suitable for evaluating the theoretical predictions of interfacial tension. Instead, the Flory Huggins interaction parameter was expressed as the sum of an enthalpic contribution, χ_H, and entropic contribution, χ_s. In the absence of reliable experimental values, a method was developed to evaluate the two contributions, based on interfacial tension data. The procedure provided an interaction parameter that is allowed to depend on molecular weight. When this approach was used, the predictions of only the new version of the square gradient theory were in good agreement with the experimental data for the influence of temperature and molecular weight on interfacial tension. However, the theory predicted the effect of polydispersity on interfacial tension only at high temperatures.     

A comparison of vapour pressure measurements of quinizarin and leuco-quinizarin via transpiration and thermogravimetry

The vapour pressure of solids can be obtained using a number of methods, including the Knudsen effusion method, the Knudsen torque-effusion method and a transpiration method. Each method has benefits and disadvantages. Reported is a comparison of vapour pressure data for two compounds, quinizarin and leuco -quinizarin, using a transpiration method and a recently developed method based on thermogravimetry. Thermogravimetry provided vapour pressure–temperature dependence data for each compound with expediency and in agreement with the transpiration method.     

Field-Testing of Methyl Salicylate for Recruitment and Retention of Beneficial Insects in Grapes and Hops

Evidence for recruitment and retention of beneficial insects in grapes and hops using controlled-release dispensers of methyl salicylate (MeSA), a component of herbivore-induced volatile blends, is presented. In a replicated experiment conducted in a juice grape vineyard, sticky cards in blocks baited with MeSA captured significantly greater numbers of five species of predatory insects (Chrysopa nigricornis, Hemerobius sp., Deraeocoris brevis, Stethorus punctum picipes, Orius tristicolor) than unbaited blocks. Four insect families (Syrphidae, Braconidae, Empididae, Sarcophagidae) were also significantly more abundant in the MeSA-baited blocks, as indicated by sticky card captures. Canopy shake samples and sticky card monitoring conducted in a MeSA-baited, unsprayed hop yard indicated development and maintenance of a beneficial arthropod population that was nearly four times greater than that present in an unbaited reference yard. Four times as many S. punctum picipes and six times as many O. tristicolor were sampled in the MeSA yard. Similar contrasts in abundance of these predators and others were apparent when compared with levels recorded in the yard in previous years. The large population of predatory insects in the MeSA-baited hop yard was associated with a dramatic reduction in spider mite numbers, the major arthropod pest of hops, in late June, and subeconomic populations were maintained for the rest of the season. The evidence presented here is highly suggestive that the use of controlled-release MeSA in a crop could increase recruitment and residency of populations of certain beneficial insects. This strategy may have the potential to enhance the efficacy and reliability of conservation biological control in crop pest management.     

The Discovery of Phenylbenzamide Derivatives as Grb7‐Based Antitumor Agents

Grb7 is a non‐catalytic protein, the overexpression of which has been associated with the proliferative and migratory potentials of cancer cells. Virtual screening strategies involving a shape‐based similarity search, molecular docking, and 2D‐similarity searches complemented by experimental binding studies (Thermofluor and isothermal titration calorimetry) resulted in the identification of nine novel phenylbenzamide‐based antagonists of the Grb7 SH2 domain. Moderate binding affinities were observed, ranging from K_d=32.3 μM for lead phenylbenzamide NSC 104999 ( 1 ) to K_d=1.1 μM for a structurally related compound, NSC 57148 ( 2 ). Deconvolution of the affinity data into its components revealed differences in lead binding, from being entropy based (lead 1 ) to enthalpically driven (NSC 100874 ( 3 ), NSC 55158 ( 4 ), and compound 2 ). Finally, the lead compound 1 was found to decrease the growth of MDA‐MB‐468 breast cancer cells, with an IC₅₀ value of 39.9 μM . It is expected that these structures will serve as novel leads in the development of Grb7‐based anticancer therapeutics.     

Aqueous poly(urethane–urea) dispersions and cast films based on m‐TMXDL. 1. Structure–property relationships

Aqueous poly(urethane–urea) dispersions were prepared from polycaprolactone diol, α,α,α′,α′‐tetramethyl‐1,3‐xylylene diisocyanate (m‐TMXDI) and α,α‐dimethylol propionic acid (DMPA) using a prepolymer mixing process. In the process, polyurethane prepolymers were neutralised with triethylamine and the chains extended in water with either hydrazine, 1,2‐ethylene diamine or 1,2‐propylene diamine. For comparison, some samples were prepared from a more commonly used diisocyanate, isophorone diisocyanate (IPDI). Dispersion characteristics and basic structure–property relationships of the cast films were determined. m‐TMXDI provided some advantages over IPDI in the preparations since its use gave lower prepolymer viscosities and better resistance to elevated temperatures. Films prepared from m‐TMXDI dispersions exhibited considerably lower values of Young's modulus and hardness and higher elongations at break than those prepared from IPDI‐based dispersions for analogous compositions, whereas differences in the average particle sizes or viscosities of the dispersions were only small. When the DMA content was varied, the dispersions and cast films of m‐TMXDI‐based systems showed similar changes as are known to occur in IPDI‐based systems: as the DMPA content was increased, the average particle size of the dispersions decreased and the viscosity increased, and for the cast films, the Young's modulus and tensile strength increased and the maximum elongation at break decreased. Changing the chain‐extension agent from hydrazine to 1,2‐ethylene diamine, to 1,2‐propylene diamine and had little effect on the particle size of the dispersions, but increased the Young's modulus and hardness of the respective cast films. Molar masses of the chain‐extended polymers were unexpectedly low. DSC analysis of cast films indicated that the degree of crystallisation of the soft or hard domains was low. © 2002 Society of Chemical Industry     

Blends of natural rubber and polyurethane latices studied by 1H wideline and 13C MAS solid‐state NMR

¹H wideline and ¹³C magic‐angle spinning NMR have been used to study the morphology and dynamics of latex‐cast and solution‐cast film blends of natural rubber (NR) and a polyurethane (PU) based on poly(?‐caprolactone) diol and isophorone di‐isocyanate. ¹H T₁ and T_1ρ relaxation times have been measured, and the extent of interpenetration of the NR and PU constituents has been monitored using the Goldman–Shen technique. The NMR spectra and relaxation properties indicated that the NR and PI constituents largely occupy separated domains on a distance scale of >10 nm. The Goldman–Shen experiments indicated that there was slightly greater contact between NR and PU in the solution‐cast samples than in the latex‐cast. The tensile properties of the films have been measured. The tensile strength and initial Young's modulus pass through a maximum at a PU content of about 50 wt%. © 2002 Society of Chemical Industry     

Effect of plasticizers on the thermal decomposition of chlorinated polyvinylchloride

Plasticized samples of chlorinated polyvinylchloride (CPVC) were investigated by using thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). Three different plasticizers were studied, namely, dioctyl phthalate (DOP), alkyldiaryl phosphate ester (Santiciser 2148), and triaryl phosphate ester (Reofos 50). TG experiments in nitrogen showed one major decomposition stage, involving dehydrochlorination, and minor pyrolysis reaction of the hydrocarbon residue. In contrast to the three stages previously reported to occur in the nonplasticized‐stabilized CPVC, TG analyses in air showed two distinctive decomposition stages for the plasticized CPVC samples. The DOP system provided a suggestion of a third stage. The first decomposition stage was due not only to the loss of all the chlorine present, but also to loss of the plasticizer or its decomposition products. The second decomposition stage was mostly due to char oxidation, the char being formed almost exclusively from the DCE and VDC units in CPVC polymer. DSC results showed that in the presence of nitrogen, there was no significant plasticizer effect on the thermal decomposition behavior of CPVC up to about 330°C, while in air the DSC traces also show no significant differences below 400°C. The two phosphate plasticizers showed no significant differences in their effect on the thermal decomposition behavior of CPVC under the same experimental conditions. It is believed that P₂O₅ and polyphosphoric acid are among the main constituents of the residua. These would impart a protective glassy surface to the char. This will facilitate effective flame retardant action. This preliminary conclusion is based on the premise that the more stable the char layers are, the more resilient will be the protective layer, and consequently, the better the flame retardant effect. J. VINYL ADDIT. TECHNOL., 11:21–27, 2005. © 2005 Society of Plastics Engineers     

Iron antimony oxide selective oxidation catalysts – an inelastic neutron scattering study

The inelastic neutron scattering spectra of allyl iodide (3-iodopropene, CH₂=CHCH₂I) and allylpalladium chloride, and allyl iodide dosed onto activated iron(III) oxide and iron antimonate catalysts at room temperature have been determined to characterise the adsorbed allyl species. The spectra are energy loss vibrational spectra in the range 16–4000 cm⁻¹. Allyl iodide is not decomposed on the surface and interacts through the localised C = C bond, more strongly with iron antimonate than with iron(III) oxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Role of Welding Parameters Using the Flux Cored Arc Welding Process of Low Alloy Steels on Bead Geometry and Mechanical Properties

Welding parameters have direct effects on the bead geometry, microstructure, and mechanical properties of low alloy steels. A series of experiments have been carried out to examine some of these parameters using the flux cored arc welding process (FCAW). In this article, an experimental study was conducted to investigate the influence of welding parameters in FCAW process particularly welding voltage and travel speed on weld bead dimensions. The study also includes the effects of bead overlap and deposition sequence on the parent material and the heat-affected zone (HAZ) properties. It was found that an increase in the welding voltage leads to an increase in the weld bead width, and the increase in the welding traverse speed leads to a decrease in the weld bead width. When studying the bead overlap percentages, it was found that the 50% bead overlap can be considered to be practically a better option than the higher percentages of bead overlap (i.e., 70-90%). The experimental investigation of studying the deposition sequence showed that there were no significant differences in the microstructure, hardness, and the size of the refined HAZ between the two proposed deposition sequences. However, a significant improvement in the microstructure and the size of the refined HAZ, and a reduction in the hardness were achieved after depositing the second welding bead, irrespective of the depositing sequence.