Approaches in biotechnological applications of natural polymers

Natural polymers, such as gums and mucilage, are biocompatible, cheap, easily available and non-toxic materials of native origin. These polymers are increasingly preferred over synthetic materials for industrial applications due to their intrinsic properties, as well as they are considered alternative sources of raw materials since they present characteristics of sustainability, biodegradability and biosafety. As definition, gums and mucilages are polysaccharides or complex carbohydrates consisting of one or more monosaccharides or their derivatives linked in bewildering variety of linkages and structures. Natural gums are considered polysaccharides naturally occurring in varieties of plant seeds and exudates, tree or shrub exudates, seaweed extracts, fungi, bacteria, and animal sources. Water-soluble gums, also known as hydrocolloids, are considered exudates and are pathological products; therefore, they do not form a part of cell wall. On the other hand, mucilages are part of cell and physiological products. It is important to highlight that gums represent the largest amounts of polymer materials derived from plants. Gums have enormously large and broad applications in both food and non-food industries, being commonly used as thickening, binding, emulsifying, suspending, stabilizing agents and matrices for drug release in pharmaceutical and cosmetic industries. In the food industry, their gelling properties and the ability to mold edible films and coatings are extensively studied. The use of gums depends on the intrinsic properties that they provide, often at costs below those of synthetic polymers. For upgrading the value of gums, they are being processed into various forms, including the most recent nanomaterials, for various biotechnological applications. Thus, the main natural polymers including galactomannans, cellulose, chitin, agar, carrageenan, alginate, cashew gum, pectin and starch, in addition to the current researches about them are reviewed in this article.. }To the Conselho Nacional de Desenvolvimento Cientfíico e Tecnológico (CNPq) for fellowships (LCBBC and MGCC) and the Coordenação de Aperfeiçoamento de Pessoal de Nvíel Superior (CAPES) (PBSA). This study was supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UID/BIO/04469/2013 unit, the Project RECI/BBB-EBI/0179/2012 (FCOMP-01-0124-FEDER-027462) and COMPETE 2020 (POCI-01-0145-FEDER-006684) (JAT)

Complexes of substituted derivatives of 2-(2-pyridyl)benzimidazole with Re(I), Ru(II) and Pt(II): structures, redox and luminescence properties

N,N′-Chelating ligands based on the 2-(2-pyridyl)benzimidazole (PB) core have been prepared with a range of substituents (phenyl, pentafluorophenyl, naphthyl, anthracenyl, pyrenyl) connected to the periphery via alkylation of the benzimidazolyl unit at one of the N atoms. These PB ligands have been used to prepare a series of complexes of the type [Re(PB)(CO)3Cl], [Pt(PB)(CCR)2] (where –CCR is an acetylide ligand) and [Ru(bpy)2(PB)][PF6]2 (bpy = 2,2′-bipyridine). Six of the complexes have been structurally characterised. Electrochemical and luminescence studies show that all three series of complexes behave in a similar manner to the analogous complexes with 2,2′-bipyridine in place of PB. In particular, all three series of complexes show luminescence in the range 553–605 nm (Pt series), 620–640 nm (Re series) and 626–645 nm (Ru series) arising from the 3MLCT state, with members of the Pt(II) series being the most strongly emissive with lifetimes of up to 500 ns and quantum yields of up to 6% in air-saturated CH2Cl2 at room temperature. In the Re and Ru series there was clear evidence for inter-component energy-transfer processes in both directions between the 3MLCT state of the metal centre and the singlet and triplet states of the pendant organic luminophores (naphthalene, pyrene, anthracene). For example the pyrene singlet is almost completely quenched by energy transfer to a Re-based MLCT excited state, which in turn is completely quenched by energy transfer to the lower-lying pyrene triplet state. For the analogous Ru(II) complexes the inter-component energy transfer is less effective, with 1anthracene → Ru(3MLCT) energy transfer being absent, and Ru(3MLCT) → 3anthracene energy transfer being incomplete. This is rationalised on the basis of a greater effective distance for energy transfer in the Ru(II) series, because the MLCT excited states are localised on the bpy ligands which are remote from the pendant aromatic group; in the Re series in contrast, the MLCT excited states involve the PB ligand to which the pendant aromatic group is directly attached, giving more efficient energy transfer

The polymer physics and chemistry of microbial cell attachment and adhesion

The attachment of microbial cells to solid substrata is a primary ecological strategy for the survival of species and the development of specific activity and function within communities. An hypothesis arising from a biological sciences perspective may be stated as follows: The attachment of microbes to interfaces is controlled by the macromolecular structure of the cell wall and the functional genes that are induced for its biological synthesis. Following logically from this is the view that diverse attached cell behaviour is mediated by the physical and chemical interactions of these macromolecules in the interfacial region and with other cells. This aspect can be reduced to its simplest form by treating physico-chemical interactions as colloidal forces acting between an isolated cell and a solid or pseudo solid substratum. These forces can be analysed by established methods rooted in DLVO (Derjaguin, Landau, Verwey and Overbeek) theory. Such a methodology provides little insight into what governs changes in the behaviour of the cell wall attached to surfaces, or indeed other cells. Nor does it shed any light on the expulsion of macromolecules that modify the interface such as formation of slime layers. These physical and chemical problems must be treated at the more fundamental level of the structure and behaviour of the individual components of the cell wall, for example biosurfactants and extracellular polysaccharides. This allows us to restate the above hypothesis in physical sciences terms: Cell attachment and related cell growth behaviour is mediated by macromolecular physics and chemistry in the interfacial environment. Ecological success depends on the genetic potential to favourably influence the interface through adaptation of the macromolecular structure. We present research that merges these two perspectives. This is achieved by quantifying attached cell growth for genetically diverse model organisms, building chemical models that capture the variations in interfacial structure and quantifying the resulting physical interactions. Experimental observations combine aqueous chemistry techniques with surface spectroscopy in order to elucidate the cell wall structure. Atomic force microscopy methods quantify the physical interactions between the solid substrata and key components of the cell wall such as macromolecular biosurfactants. Our current approach focuses on considering individually mycolic acids or longer chain polymers harvested from cells, as well as characterised whole cells. This approach allows us to use a multifactorial approach to address the relative impact of the individual components of the cell wall in contact with model surfaces. We then combine these components to increase complexity step-wise, while comparing with the behaviour of entire cells. Eventually, such an approach should allow us to estimate and understand the primary factors governing microbial cell adhesion. Although the work addresses the cell–mineral interface at a fundamental level, the research is driven by a range of technology needs. The initial rationale was improved prediction of contaminant degradation in natural environments (soils, sediments, aquifers) for environmental cleanup. However, this area of research addresses a wide range of biotechnology areas including improved understanding of pathogen survival (e.g., in surgical environments), better process intensification in biomanufacturing (biofilm technologies) and new product development