Stochastic molecular descriptors for polymers. 4. Study of complex mixtures with topological indices of mass spectra spiral and star networks: The blood proteome case

The Quantitative Structure-Property Relationships (QSPRs) based on Graph or Network Theory are important for predicting the properties of polymeric systems. In the three previous papers of this series (Polymer 45 (2004) 3845-3853; Polymer 46 (2005) 2791-2798; and Polymer 46 (2005) 6461-6473) we focused on the uses of molecular graph parameters called topological indices (TIs) to link the structure of polymers with their biological properties. However, there has been little effort to extend these TIs to the study of complex mixtures of artificial polymers or biopolymers such as nucleic acids and proteins. In this sense, Blood Proteome (BP) is one of the most important and complex mixtures containing protein polymers. For instance, outcomes obtained by Mass Spectrometry (MS) analysis of BP are very useful for the early detection of diseases and drug-induced toxicities. Here, we use two Spiral and Star Network representations of the MS outcomes and defined a new type of TIs. The new TIs introduced here are the spectral moments (π_k) of the stochastic matrix associated to the Spiral graph and describe non-linear relationships between the different regions of the MS characteristic of BP. We used the MARCH-INSIDE approach to calculate the π_k(SN) of different BP samples and S2SNet to determine several Star graph TIs. In the second step, we develop the corresponding Quantitative Proteome-Property Relationship (QPPR) models using the Linear Discriminant Analysis (LDA). QPPRs are the analogues of QSPRs in the case of complex biopolymer mixtures. Specifically, the new QPPRs derived here may be used to detect drug-induced cardiac toxicities from BP samples. Different Machine Learning classification algorithms were used to fit the QPPRs based on π_k(SN), showing J48 decision tree classifier to have the best performance. These results suggest that the present approach captures important features of the complex biopolymers mixtures and opens new opportunities to the application of the idea supporting classic QSPRs in polymer sciences.     

DNA-inorganic hybrid material as selective absorbent for harmful compounds

Double-stranded DNA is one of functional polymers, but the large amounts of DNA sources, such as salmon milt and shellfish gonads, have been discarded as industrial wastes. Therefore, conversion of this discarded DNA to be a useful material would be beneficial to utilize the unique property of DNA. These materials including DNA have been prepared by mixing with the organic polymers, such as alginic acid, collagen, and chitosan. However, since these materials have consisted from entirely organic components, these do not have the mechanical strength for a material. So, we prepared the organic-inorganic hybrid materials by mixing DNA with silane coupling reagents bis(trimethoxysilylpropyl)amine or bis[(3-trimethoxysilyl)propyl]ethylenediamine. These hybrid materials with the flexibility were water-insoluble and resistant to hydrolysis by nuclease. In addition, the mechanical strength of this hybrid material was approximately twice as high as that of DNA without mixing with silane coupling reagents. Furthermore, the double-stranded DNA in the hybrid materials has been maintained in a B-form structure in aqueous solution. Thus, we demonstrated the utilization of DNA as a functional material. As a result, this material could selectively accumulate harmful DNA-intercalating compounds with the planar structure, such as dibenzo-p-dioxin, dibenzofuran, and ethidium bromide. Organic-inorganic hybrid material including double-stranded DNA has potential to serve as a useful biomaterial for medical, engineering, and environmental applications.     

Microstructure and mechanical properties of soy protein/agar blend films: Effect of composition and processing methods

The present work prepared a series of soy protein isolate/agar blend films containing 33% glycerol as plasticizer by solution casting and thermo-molding methods. The microstructure and mechanical properties of the blend films were evaluated in relation to the agar/protein ratio as well as the processing methods. Experimental results revealed that hydrogen bonding interactions existed between soy protein and agar. The casting films possessed more homogeneous interfaces compared with the molding films, leading to the superior mechanical properties than those molding films. Owing to the rigid three-dimensional network formed by the agar, the tensile strength of casting blend films was enhanced. With the increase of agar in the casting blend films, the crosslinking density increased and was responsible for the variations in tensile strength.     

Synthesis and Characterization of Linear and Tri-Block PLLA–PEG–PLLA Blends

This study was conducted to synthesize poly(L-lactide)–poly(ethylene glycol)–poly(L-lactide) triblock copolymer (PEGLA) with different poly(L-lactide) block length, and explore its applicability in a blend with linear poly(L-lactide) (3051D NatureWorks) with the intention of improving heat seal and adhesion properties at extrusion coating on paperboard. Poly(L-lactide)–poly(ethylene glycol)–poly(L-lactide) was obtained by ring opening polymerization of L-lactide using poly(ethylene glycol) (molecular weight 6000 g mol^?1) as an initiator and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy. The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology and differential scanning calorimeter. All blends containing 10 wt% of PEGLAs displayed similar zero shear viscosities to neat poly(L-lactide), while blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity. However, all blends displayed higher shear thinning and increased melt elasticity (based on tan δ). No major changes in thermal properties were distinguished from differential scanning calorimetric studies. High molecular weight PEGLAs could be used in extrusion coating with 3051D without problems.     

Isothermal and non‐isothermal crystallization of poly(L‐lactic acid)/poly(butylene terephthalate) blends

Isothermal and non‐isothermal crystallization kinetics of poly(l ‐lactic acid)/poly(butylene terephthalate) (PLLA/PBT) blends containing PLLA as major component is detailed in this contribution. PLLA and PBT are not miscible, but compatibility of the polymer pair is ensured by interactions between the functional groups of the two polyesters, established upon melt mixing. Crystal polymorphism of the two polyesters is not influenced by blending, as probed by wide‐angle X‐ray analysis. The addition of PLLA does not affect the temperature range of crystallization kinetics of PBT, nor the crystallinity level attained when the blends are cooled from the melt at constant rate. Conversely, PBT favors crystallization of the biodegradable polyester. The addition of PBT results in an anticipated onset of crystallization of PLLA during cooling at a fixed rate, with a sizeable enhancement of the crystal fraction. Isothermal crystallization analysis confirmed the faster crystallization rate of PLLA in the presence of PBT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40372.     

Modifications in stability and structure of whey protein-coated o/w emulsions by interacting chitosan and gum arabic mixed dispersions

The influence of chitosan and gum arabic mixtures on the behaviour of o/w emulsions has been investigated at pH = 3.0. The emulsion behaviour, properties and microstructure were found to be greatly dependent on the precise gum arabic to chitosan ratio. Mixing of gum arabic with chitosan leads to the formation of coacervates of a size dependent on their ratio. Incorporation of low gum arabic to chitosan weight ratios into whey protein-coated emulsions causes depletion flocculation and gravity-induced phase separation. Increasing the polysaccharide weight ratio further, a droplet network with a rather high viscosity (at low shear stress) is generated, which prevents or even inhibits phase separation. At even higher gum arabic to chitosan ratios, the emulsion droplets were immobilised into clusters of an insoluble ternary matrix. Although the emulsion droplet charge had the same sign as that of the coacervates, clusters of oil droplets in a ternary matrix were generated. A mechanism to explain the behaviour of the whey protein-stabilised o/w emulsions is described on the basis of confocal and phase contrast microscopic observations, rheological data, zeta potential measurements, particle size analysis and visual assessment of the macroscopic phase separation events.     

Semicontinuous Discharge of Non‐Newtonian Filter Cakes in Electrofiltration

A novel mode of operation for electrofiltration is presented. The newly developed operation procedure allows for cake removal without disassembling the chamber. Highly viscous filter cakes are discharged from the filtration chamber by inserting air which permits a rapid restart of the process. The cleaning time could be reduced from about 10 min to a few seconds. The semicontinuous operation is liable to full automation and allows for cake discharge and filtration in a short period of time. In successive cycles was proved that the process efficiency is maintained using the same membrane. A fully continuous system can be accomplished by assembling several units in parallel in a single filtration press.