Biodegradable synthetic and semisynthetic polymers

As a part of our continuing interest in the preparation of multifunctional polymeric materials and evaluation of their potential in pharmaceutical, medical and environmental fields, a survey on new polymeric systems of synthetic and semisynthetic origin, susceptible to bioerosion and/or biodegradation attack is presented. In particular, attention has been focused on the design, preparation and characterization of the following classes of hydrophilic and/or water-soluble polymeric materials: hydroxyl-containing poly(ester)s, hydroxyl-containing poly(amide)s, hydrophilic polymers containing carboxylic groups, perhydroxylated oligo- and poly(saccharide)s, oxidized poly(saccharide)s, and hybrid polymeric materials based on blends of carboxyl-containing synthetic polymers and proteins. The rationale of the research activity undertaken over the years is illustrated by focusing on some specific achievements of practical significance.     

Wheat gluten films obtained by compression molding

Edible films based on plasticized wheat gluten protein were prepared by intensive mixing followed by compression molding. The effects of water and glycerol, which were selected as plasticizers for the wheat gluten, as well as the processing conditions (mixing time and molding temperature) on the physical and mechanical properties of the films were evaluated. The resulting films were characterized in terms of moisture sorption, total soluble matter, water vapor permeability, dynamic mechanical and tensile properties. It was found that plasticizer type and concentration had a dominating effect on mechanical properties and WVP, while other physical properties remain almost non-affected. Moreover, the effect of the added plasticizer (glycerol) on the film properties strongly depends on natural presence of water in commercial gluten (9% as is). On the other hand, the pressing temperature affected the final properties of the films more than the mixing time because the former influences the final cross-linking degree of the protein network. Processing temperatures higher than 100 °C led to darker films that would be discarded by consumers if they were used as food packaging.     

Abiotic and biotic degradation of oxo-biodegradable polyethylenes

Conventional polymeric materials accumulate in the environment due to their low biodegradability. However, an increase in the biodegradation rate of these polymers may be obtained with the addition of pro-degrading substances. This study aimed to evaluate abiotic and biotic degradation of polyethylenes (PEs) using plastic bags of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) formulated with pro-oxidant additives as test materials. These packaging materials were exposed to natural weathering and periodically analyzed with respect to changes in mechanical and structural properties. After a year of exposure, residue samples of the bags were incubated in substrates (compost of urban solid waste, perlite and soil) at 58 °C and at 50% humidity. The biodegradation of the materials was estimated by their mineralization to CO₂. The molar mass of the pro-oxidant-activated PE decreased and oxygen incorporation into the chains increased significantly during natural weathering. These samples showed a mineralization level of 12.4% after three months of incubation with compost. Higher extents of mineralization were obtained for saturated humidity than for natural humidity. The growth of fungi of the genera Aspergillus and Penicillium was observed on PE films containing pro-oxidant additives exposed to natural weathering for one year or longer. Conventional PE films exposed to natural weathering showed small biodegradation.     

A simple method suitable to test the ultimate biodegradability of environmentally degradable polymers

A straightforward experimental set-up derived from the Biometer Flask previously utilized for experiments of pesticides biodegradation, has been adopted for testing the ultimate biodegradability of natural, synthetic and semi-synthetic polymeric materials on solid substrates such as soil and mature compost. The use of these whole substrates as incubation media in respirometric experiments, may negatively affect the accuracy of the test due to the large amount of carbon dioxide developed from the blanks, especially in the presence of specimen degrading at low or moderate rates. In the present test procedure soil and compost samples are diluted with perlite, a naturally occurring inert aluminum silicate widely utilized in horticultural applications, in order to ensure optimal conditions for the microbial growth while reducing the carbon dioxide emissions from the blanks. The results so far reported clearly indicate that the adopted procedure is extremely valuable and versatile for the appreciation of even subtle differences in the biodegradation rate of different polymeric materials, as well as for long-term degradation experiments.     

Multifunctional bioerodible/biodegradable polymeric materials

As a part of our continuing interest in the preparation of multifunctional polymeric materials and evaluation of their potential in biomedical and environmental field, a survey on new polymeric systems susceptible to bioerosion and/or biodegradation attack is presented. In particular attention has been focused on the preparation and characterization of the following classes of polymeric materials: 1) hydroxyl-containing polyesters; 2) functionalized cyclodextrins; 3) hydrophilic polymers containing carboxylic groups; 4) hydrogels for the release of phytodrugs; 5) hybrid polymeric materials; 6) synthetic and semisynthetic polyfunctional polymeric materials for the removal of uremic toxins. A few examples of the use of these polymers in the controlled release of drugs and as coadjuvants in the chronic renal failure treatment will be also presented.     

Biodegradable composite films based on waste gelatin

Gelatin, a naturally occurring polymer, is currently used in various applications comprising manufacturing of pharmaceutical products, x-ray and photographic films development and food processing. However, gelatin scraps generated in the different manufacturing processes may constitute a concern for the environment. Basically speaking, waste disposal deriving from plastics based on synthetic as well as semisynthetic polymeric materials, is becoming an increasingly difficult problem for their unfavorable volume-to-weight ratio and extremely wide variability of type, shape and composition of post consume plastic items that hinder the way to a general unique option for a simple and economically feasible management. As a partial solution to the global issue of plastic waste, in recent years much interest has been devoted to the formulation of environmentally degradable plastic items. Biodegradable mulching films were formulated from blends and composites based on waste gelatin and other natural waste such as sugarcane bagasse or synthetic materials such as PVA. Also, crosslinked films were produced using external or inherent crosslinker. The films were produced either by casting method or spraying on soil surface. The composites were submitted to biodegradation trials. The results showed that the films were biodegradable and the crosslinking could delay and predeterminate their biodegradation rate and extent.     

Development of a multiplex DNA-based traceability tool for crop plant materials

The authenticity of food is of increasing importance for producers, retailers and consumers. All groups benefit from the correct labelling of the contents of food products. Producers and retailers want to guarantee the origin of their products and check for adulteration with cheaper or inferior ingredients. Consumers are also more demanding about the origin of their food for various socioeconomic reasons. In contrast to this increasing demand, correct labelling has become much more complex because of global transportation networks of raw materials and processed food products. Within the European integrated research project ‘Tracing the origin of food’ (TRACE), a DNA-based multiplex detection tool was developed—the padlock probe ligation and microarray detection (PPLMD) tool. In this paper, this method is extended to a 15-plex traceability tool with a focus on products of commercial importance such as the emmer wheat Farro della Garfagnana (FdG) and Basmati rice. The specificity of 14 plant-related padlock probes was determined and initially validated in mixtures comprising seven or nine plant species/varieties. One nucleotide difference in target sequence was sufficient for the distinction between the presence or absence of a specific target. At least 5% FdG or Basmati rice was detected in mixtures with cheaper bread wheat or non-fragrant rice, respectively. The results suggested that even lower levels of (un-)intentional adulteration could be detected. PPLMD has been shown to be a useful tool for the detection of fraudulent/intentional admixtures in premium foods and is ready for the monitoring of correct labelling of premium foods worldwide.     

The biodegradation of poly-β-(hydroxybutyrate), poly-β-(hydroxybutyrate-co-β-valerate) and poly(ε-caprolactone) in compost derived from municipal solid waste

Understanding the behavior of polymeric materials, particularly their biodegradation, is fundamental for solving problems in the management of environmental residues. In this work, we used a monitoring system based on an aerobic biodegradation technique known as the Sturm test to investigate the biodegradation of poly-β-(hydroxybutyrate), poly-β-(hydroxybutyrate-co-β-valerate) and poly(ε-caprolactone), in compost derived from municipal solid waste. The thermal analysis of these polymers was done using differential scanning calorimeter. The melting temperature and crystallinity were also determined. The results showed that poly-β-(hydroxybutyrate) degraded faster than the other two polymers, probably because the chemical structure of this polymer made attack by microorganisms easier.     

ABSORBABLE SURGICAL SUTURES

Abstract

Sutures are sterile’ filaments used to close wounds and are made of either absorbable or nonabsorbable materials. The choice of suture materials for surgery is made mainly on the basis of biocompatibility and mechanical properties. The biological interaction with the tissues is considered from the point of view of the inflammatory reaction caused. An ideal suture is one that does not merely avoid negative reactions but also keeps a sterile environment and stimulates the process of healing. An absorbable suture is one which is degraded in body tissues to soluble products and disappears from the implant site, usually within 2 to 6 months. A nonabsorbable suture is resistant to biodegradation, becomes encapsulated in a fibrous sheath, and remains in the tissue as a foreign body unless it is surgically removed (e.g., skin sutures) or extruded. Sutures may be fabricated as monofilaments or multifilaments. The latter are generally braided but sometimes twisted or spun and may be coated with wax, silicone, or other polymers to decrease capillarity and improve handling properties. Hoffman [1] presented a survey on the medical applications of synthetic and natural fibrous materials made from such polymers as poly-(fluorocarbons), polyamides, polyolefins, polypeptides, and polysaccharides which are both nonbiodegradable or slowly biodegrad-ing and biodegradable fibers. Frazza [2] prepared a review on mechanical properties and sterilization of natural and synthetic absorbable and nonabsorbable suture materials. The present paper is a review on materials that have been in recent times as absorbable sutures     

Large Continuous Mechanical Gradient Formation via Metal–Ligand Interactions

Mechanical gradients are often employed in nature to prevent biological materials from damage by creating a smooth transition from strong to weak that dissipates large forces. Synthetic mimics of these natural structures are highly desired to improve distribution of stresses at interfaces and reduce contact deformation in manmade materials. Current synthetic gradient materials commonly suffer from non‐continuous transitions, relatively small gradients in mechanical properties, and difficult syntheses. Inspired by the polychaete worm jaw, we report a novel approach to generate stiffness gradients in polymeric materials via incorporation of dynamic monodentate metal–ligand crosslinks. Through spatial control of metal ion content, we created a continuous mechanical gradient that spans over a 200‐fold difference in stiffness, approaching the mechanical contrast observed in biological gradient materials.     

Recycling of waste from polymer materials: An overview of the recent works

Polymer recycling is a way to reduce environmental problems caused by polymeric waste accumulation generated from day-to-day applications of polymer materials such packaging and construction. The recycling of polymeric waste helps to conserve natural resource because the most of polymer materials are made from oil and gas. This paper reviews the recent progress on recycling of polymeric waste form some traditional polymers and their systems (blends and composites) such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and introduces the mechanical and chemical recycling concepts. In addition, the effect of mechanical recycling on properties including the mechanical, thermal, rheological and processing properties of the recycled materials is highlighted in the present paper.     

Biodegradation of chemically modified wheat gluten-based natural polymer materials

Biodegradation of a series of chemically modified thermally processed wheat gluten (WG)-based natural polymers were examined according to Australian Standard (AS ISO 14855). Most of these materials reached 93-100% biodegradation within 22 days of composting, and the growth of fungi and significant phase deformation were observed during the process. Chemical crosslinking did slow down the rate or reduce the degree of the biodegradation with different behaviours for different modified systems. The segments containing structures derived from the reactions with additives such as tannin or epoxidised soybean oil remained in the degradation residues while the glycidoxypropyl trimethoxysilane agent produced ∼20% un-degraded residues containing silicon-crosslinking structures. The biodegradation rate of each component of the materials was also different with the protein and starch components degraded fast but lipid degraded relatively slowly.     

Towards a universal polymer backbone: design and synthesis of polymeric scaffolds containing terminal hydrogen-bonding recognition motifs at each repeating unit

Polymers containing terminal hydrogen-bonding recognition motifs based on diaminotriazine and diaminopyridine groups in their side chains for the self-assembly of appropriate receptors have been prepared by ring-opening metathesis polymerization (ROMP) of norbornenes. A new synthetic method for the preparation of norbornene monomers based on pure alkyl spacers is introduced. These monomers show unprecedented high reactivity using ROMP. To suppress self-association of diaminotriazine-based polymers, polymerizations were run in presence of N-butylthymine. The butylthymine acts as a protecting group via self-assembly onto the hydrogen-bonding sites of the polymeric scaffold, thereby solubilizing the polymer. Diaminopyridine monomers do not require the presence of a protecting group due to their low propensity to dimerize. In addition, they exhibit a high affinity for hydrogen-bonded receptors on both monomeric and polymeric level. These polymers present our first building blocks towards the design and synthesis of a "universal polymer scaffold".     

Experimental and DFT analysis of onion peels for its inhibition behavior against mild steel corrosion in chloride solutions

Natural materials are good options for being used as inhibitors due to their high biodegradability, reasonable cost, easiness in use and high efficiency. In this regard, waste natural materials are very useful because they have all the properties of natural materials and easily available at very low cost (almost free). This work reports a similar kind of waste natural materials namely onion peels. The water extract of onion peels (WEOP) is characterized by UV–vis spectroscopy (UVS) and FTIR spectroscopy (FTIS). WEOP is tested for corrosion inhibition of mild steel (MS) in 1 M NaCl by various techniques like typical weight loss measurements (WLM), open circuit potential (OCP) curves, Tafel polarization (TP) curves, electrochemical impedance spectroscopy (EIS) and surface scanning microscopy (SEM). The maximum inhibition of mild steel corrosion is 90% (WLM). The reason of inhibition based on experimental analysis is proposed as adsorption of extract molecules on MS, which is found true in SEM images and Langmuir isotherm study. The WEOP is also examined by density functional theory principles, which recommends that the extract molecules can be easily adsorbed on MS and can stop corrosion of MS in NaCl solutions. Based on investigation, a schematic is introduced for compact explanation.     

Swelling and Reswelling Characteristics of Cross-Linked Poly(vinyl alcohol)/Chitosan Hydrogel Film

Poly(vinyl alcohol) (PVA), hydrogel was prepared by using glutaraldehyde as a cross-linking agent. The blend semi-synthetic hydrogel film, consisting of PVA and chitosan, was prepared from a solvent-casting technique and characterized for their intermolecular interactions using infrared method. The swelling and reswelling behaviors, as well as mechanical properties of the synthetic and semi-synthetic gels were examined by weighing and tensile testing, respectively. Cross-linking the two types of polymer with glutaraldehyde produces a film with lower crystallinity and smaller swelling and reswelling degrees, but having improved mechanical properties. Also, the two types of films show a pH-dependent swelling characteristic. It was found that, the reswelling properties of synthetic hydrogels can be improved by blending PVA with certain ratio of natural polymer. This blending film, can be improve sandy soil properties for cultivation, such as, controlled release of water.     

Crystallization,Mechanical and Flame-retardant Properties of Poly(lactic acid) Composites with DOPO and DOPO-POSS

Poly(lactic acid)(PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and DOPOcontaining polyhedral oligomeric silsesquioxane(DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry(DSC), X-ray diffraction(XRD), tensile testing, thermogravimetric analysis(TGA), limiting oxygen index(LOI),and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis(TGA) tests showed that the PLA,DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate(p-HRR).It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.     

Effects of synthetic and natural zeolites on morphology and thermal degradation of poly(lactic acid) composites

Poly(lactic acid) (PLA) composites containing 5 wt% synthetic (type 4A) and natural (chabazite) zeolites were prepared using extrusion/injection molding. Morphological, structural, and thermal properties of composites were investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). DSC results revealed that the glass transition and melting temperatures were not significantly changed; however, the incorporation of both type 4A and chabazite zeolites enhanced the nucleation of PLA crystallites as well as increased the percent crystallinity. Thermal degradation properties of PLA and PLA/zeolite composites were studied by non-isothermal thermogravimetric analysis (TGA) in nitrogen atmosphere. TGA results showed that at temperatures above 300 °C, PLA/type 4A synthetic zeolite composites were thermally decomposed more easily than the PLA and PLA/chabazite natural zeolite composites. The apparent activation energies of thermal degradation of PLA and PLA/zeolites composites estimated using both the Flynn-Wall-Ozawa and Kissinger methods followed the same order: PLA/type 4A < PLA/chabazite < PLA.     

Synthesis and Characterization of Polypyrrole Nanoparticles and Their Nanocomposites with Poly(propylene)

Summary: Conducting polypyrrole (PPy) nanoparticles were synthesized via microemulsion polymerization. PP/PPy nanocomposites were prepared by melt-mixing of polypyrrole with polypropylene (PP) and processed with injection molding. Tensile tests have revealed that increasing amount of PPy increased the strength and the stiffness of the nanocomposite while limiting the elongation of PP. Thermal gravimetric analysis has showed that incorporation of PPy nanoparticles has improved the thermal stability of the nanocomposites. Increasing amount of PPy nanoparticles increases the conductivity of nonconductive PP up to 2,4.10⁻⁴ Scm⁻¹. The same techniques were used to characterize nanocomposites containing 2% w dispersant. Composites prepared with dispersant have involved smaller dimension PPy nanoparticles and exhibited improvement in some mechanical and thermal properties.     

在低频振动场中注射成型HDPE试样的力学性能及其形态控制

利用自行研制的低频振动注射实验装置探讨HDPE振动注射试样力学性能和微观形态之间的关系 .实验中对常规注射和振动注射成型的试样力学性能和微观形态进行了对比实验 .SEM实验结果显示 ,振动注射制件芯层的形态由常规注射的球晶转变为垂直于振动波传递方向排列的片晶结构 ,在剪切层中同时存在串晶或柱状堆砌的片晶结构 .频率的改变 (0 相似文献   

How the biodegradability of wheat gluten-based agromaterial can be modulated by adding nanoclays

The objective of this work was to investigate the influence of clay nanoparticles on the biodegradability of wheat gluten-based materials through a better understanding of multi-scale relationships between biodegradability, water transfer properties and structure of wheat gluten/clay materials. Wheat gluten/clay (nano)composites materials were prepared via bi-vis extrusion by using an unmodified sodium montmorillonite (MMT) and an organically modified MMT. Respirometric experiments showed that the rate of biodegradation of wheat gluten-based materials could be slowed down by adding unmodified MMT (HPS) without affecting the final biodegradation level whereas the presence of an organically modified MMT (C30B) did not significantly influence the biodegradation pattern. Based on the evaluation of the water sensitivity and a multi-scale characterization of material structure, three hypotheses have been proposed to account for the underlying mechanisms. The molecular/macromolecular affinity between the clay layers and the wheat gluten matrix, i.e. the ability of both components to establish interactions appeared as the key parameter governing the nanostructure, the water sensitivity and, as a result, the overall biodegradation process.