Biguanide-, imine-, and guanidine-based networks as catalysts for transesterification of vegetable oil

Polycationic systems based on poly(hexamethylene biguanide) (PHMBG), branched polyethyleneimine (PEI) and poly(N-vinylguanidine) (PVG) have been evaluated as heterogeneous catalysts for the transesterification of sunflower oil by methanol. Insoluble networks are synthesized via cross-linking of PHMBG by either 4,4′-methylenebis(N,N-diglycidylaniline) or polyisocyanate prepolymer, PEI with sebacoyl chloride, and PVG with 1,4-butanediol diglycidyl ether. PHMBG and its cross-linked networks appeared to be remarkably efficient catalysts, enabling 80–100% triglyceride conversion within 0.5 h at 70 °C. PEI-based networks catalyzed triglyceride transesterification with rates 8- to 12-fold slower than their PHMBG-based counterparts. The PVG-based networks, which were devoid of hydrophobic moieties, appeared to be inefficient catalysts due to limited accessibility of the basic guanidine groups to reactants. The PHMBG networks were shown to be recyclable by a simple centrifugal filtration. After 15 cycles of recovery and reuse, only 10–15% decline in performance was observed.     

Epoxidizable Fatty Amide–Phenol Conjugates

This paper reports the synthesis of a series of novel compounds where carboxylic acids have been linked to a phenol through amidomethyl units. For instance, one, two, or three fatty acids have been selectively appended to the phenol in yields above 75%. The fatty acid used was oleic acid, which was subsequently epoxidized. Other functional groups, such as amino acids, can be incorporated in these compounds. Examples of monomers that are suitable for polymerization were also prepared: one acrylamide, one styrene derivative, and two types of AB₂ diamino acids, all of which contain oleic units that are sites for epoxidation and crosslinking. Fatty acid aryl ethers were prepared using hydroxy fatty acids. These molecules are intended to serve as augmented analogues of epoxidized vegetable oil. Their amide groups should lead to intermolecular aggregation through hydrogen bonding, and the option to covalently include other functional groups may permit tuning of the macroscopic materials properties of films, coatings, or solids constructed from them.     

Sustainable energy development: performance and prospects

Concerns about sustainability, and the harsh realities of environmental catastrophe, can be traced back at least 4000 years. This paper points out how human pressures on the surrounding environment have had severe consequences over this period, coal burning has had adverse consequences traceable over the past 750 years, and the adverse environmental impacts of using other fossil fuels have aroused attention more recently. Heightened awareness of the need for sustainable development is a modern development, evident in international and national debates since the early 1970s. With the Brundtland Commission report published in 1987 came a framework for sustainable energy development. However, performance under the four elements of that framework have been almost uniformly disappointing. Fossil fuel use has continued to rise; renewable energy use has made insufficient inroads; waste and inefficiency in energy usage continues to be far too high; too many people remain without modern energy services or are exposed to severe pollution in the home and local atmosphere; there are mounting concerns about the conventional oil resource base—and future supplies and prices of oil and natural gas; greenhouse gas emissions continue to rise and evidence of human-induced climate change continues to mount. Indices of national environmental performance suggest no country is performing adequately; population, housing and transportation pressures result in greater pollution, loss of natural habitats, and species reduction; and poor governance is frequently cited as a major cause of poor environmental performance. The prospects for sustainable energy are bleak on current trends.     

Release of fluorescent markers from phase‐separated gelatin‐maltodextrin hydrogels

Genipin‐crosslinked gelatin‐maltodextrin phase‐separated hydrogels consisting of gelatin‐continuous or bicontinuous microstructures were developed to regulate swelling and release behavior of four fluorescent markers of varying molecular weights [(fluorescein (332 Da) and FITC‐dextrans (FD) (4000–250,000 Da)]. Bicontinuous hydrogels showed significantly greater swelling than gelatin‐continuous hydrogels under all conditions (at pH 1.5 and 7.4 and three genipin/gelatin crosslinking ratios) (P < 0.05). With both microstructures, fluorescein showed the largest release rate and total release followed by FD 4000 Da, FD 40,000 Da, and FD 250,000 Da (P < 0.05). Marker molecular weight, pH, and crosslink ratio all affected the rate and amount of release. The mode of transport for the solvent and all markers was Fickian or slightly anomalous, with diffusional exponent (n) values ranging from 0.35 to 0.64. These results demonstrated that with the proper combination of crosslink density, solvent pH, and microstructure, hydrogels with a specified swelling behavior may be developed. This, coupled with a marker of appropriate size, can lead to controllable levels and rates of release. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

pH-change protective PB-b-PEO polymersomes

Poly(butadiene)-b-poly(ethylene oxide) vesicles were successfully loaded with hydrophilic dye Phloxine B. Dye addition during vesicle formation leads to Phloxine B encapsulated inside the water filled vesicle core as well as to freely diffusing dye molecules. The removal of uncapsulated substrate involves time consuming methods like dialysis or harsher methods like ultra filtration or selective precipitation, posing the risk of irreversible sample manipulation. Here used Phloxine B as pH sensitive fluorescence indicator allows the characterization of hydrophilic loading without separation procedure by adjusting the pH value. Additionally membrane blocking efficiency can be studied by time dependent fluorescence measurements. Cryogenic TEM studies showed that the self-assembled structure remained unchanged when the hydrophilic dye was incorporated within the vesicles. Fluorescence microscopy imaging proved the encapsulation of the hydrophilic dye inside the core volume. The combination of fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS) measurements as ensemble methods confirmed those results additionally.     

Prior-to-failure extension of flaws under monotonic and pulsating loadings

An equation governing the prior to failure crack propagation is proposed. For a rate-sensitive solid containing two-dimensional crack and subject to the tensile mode of fracture the differential equations are integrated numerically for the loads increasing monotonically in time. The resulting integral curves gs = σ(l) and l= l(t), i.e. load vs crack length and length vs time, indicate that the growth of cracks in the subcritical range is strongly rate dependent.The fatigue growth, viewed as a sequence of slow growth periods, is simulated on EAI 380 analogue computer. The fourth power law proposed by Paris is confirmed only within certain range of high-cycle fatigue propagation and for a rate-insensitive solid. Otherwise, that is for a more pronounced rate dependency induced by viscosity of a solid and/or in the proximity of the final instability point the growth is markedly enhanced. For sufficiently small ratios of the applied stress intensity range ΔK to the toughness K_c, the suggested fatigue growth law consists of two terms, i.e.

$\text{d}\text{l}\text{d}\text{n}\text{=}\text{l}{}_1\text{12}\text{4}\text{ΔK}\text{K}{}_{\mathrm{c}}{}^4\text{+Cf}{}^{\mathrm{?1}}\text{ΔK}\text{K}{}_{\mathrm{c}}{}^2\text{, l}{}_1\text{=}\text{πK}{}^2{}_{\mathrm{c}}\text{8Y}{}^2$

First term is the familiar Paris expression while the second one accounts for the rate-dependent contribution; f denotes frequency and Y is the yield strength. Rate-sensitivity C is defined by eq. (1.13).