A. IMMOBILISING CONSTRUCTION OF PHYSICI-CHEMICAL PROPERTIES OF SUPERMOLECULAR

CONSTRUCTS OF NATURAL POLYSACHARIDES AND TREIR AMORPHOUS FRACTIONS VIA BIOCHEMICAL

AND PHYSICO-CHEMICAL MODIFICATION.

B. BARRIER FUNCTIONAL PACKAGING FOR HUMAN AND ANIMAL BODY, PRESERVATION OF AGRARIAN PLANTS AND HARVEST CROPS LOCAL BIOACTIVE

BARRIER.

Dr. Chemistry of material, Oleg V. AnokhinHead of Information-Organisational Sector

Centre for International Co-operation

Dr.,Prof, Tatiyna S. ShostakKiev National University of Technologies & Design

Kiev -2009

Inefficient use of natural resources for the current millennium aggravated the problem of environment conservation. The most relevant objective proves to be a development of new technologies which facilitate the creation of new environmentally sound products and conservation of natural resources.

Most of the materials used by people contain synthetic or natural fibres of different nature and structure. Moreover, according to experience, using natural materials involves usually about 50% of their mass. Cellulose having a number of physical/chemical properties appears to be the most widely used among natural fibres.We know that natural cellulose fibres are of no equilibrium structure which is heterogeneous over a cross section. Photo.

This structure defines the morphology of fibre and energy of interaction between the structural elements. The properties of fibres and anisotropy of these properties are largely dependent on supramolecular (nanolevel of structural organization). This study offers the development of new approaches, (model designs) and tools, as a mechanism for development of new technologies. Therefore, it is necessary to carry out a system of researches for studying the processes of structural changes during processing of native cellulose fibres. Development of such scientific instrumentation is associated with the consideration of molecular processes proceeding during secondary crystallization.

Systematisation and coordinated arrangement of realization of processes of secondary crystallization are the very objective of these researches. Without doubt, such processes as relaxation of internal stresses with specially selected plasticizers at elevated temperatures and their components; alternating thermal “swaying” of supramolecular and amorphous compositions; impact of pressure bring about the change of properties over a wide range.

Accordingly the phased consideration of such complex multifunction systems starts with models of constant pressure and constant volume with detailed consideration of each phase and the improved technologies being offered.

In the initial phase we plan modelling exercises to transfer already existing supramolecular compositions of polysaccharides to unsteady state via their formation from existing biological entities, represented by any plant with different composition and types of structural formations of cellulose and with different speed of its synthesis. (option for future production).

The objective of the first phase is a possibility to control the structural changes which, according to the preliminary studies, can reduce the instability in a number of fibre properties.

One of the basic peculiarities of this study is an effort being taken to perform a system modification of the properties of supramolecular structure of fibres at the phase immediately upon maturation of plant or (in the long term) detection of the moment the most favourable in structure formation for further directed modification of supramolecular structure.

Up to present these processes were performed by the nature itself and this is not just a month of “nature processing” due to complexity or just impossibility of removing products from amorphous phase. Photo (leaching out). While the components of this amorphous phase are unique in their chemical, physical/chemical, biochemical, general medical (presence of fatty acids), therapeutic, germicidal, immunoactive properties and other unique natural compositions. Tables - well-known comparative charts: plant — chemistry. Photo.

H2O

NO

2

NO

2

This study offers a new approach to the development of “tools” capable to extend the possibilities of rational exploitation of physical and chemical substances from natural fibres by means of fractionation of natural polysaccharides. The above mentioned tasks can be realized using substances with the maximum zwitterionic molecular structure having the pronounced cation acceptor properties. The authors propose the creation of a combined, bioactive, steady inhibiting solvent with signified properties of penetration.

We offered surface active agents as one of the basic "tools". foto.

Further after the following is employed: А) zwitterionic agents, B) wetting hysteresis, C) solubilization processes, D) salting out + sublimation, E) salting out at supramolecular level of purified compositions of polysaccharides. Photo. Langmuir palisade.

• In the preceding studies, functional properties of surface active agents were activated and modified and as a result a possibility of realization of solution process for common and complex salt was created – dilution of inorganic and organic compounds, formation of adducts and associates.

• Science team developed an approach for creation of universal solvent having the above mentioned properties on the basis of the agent with very frank cation acceptor properties. Photo #1 Photo #2 + -

• As a result a compound is created, being less toxic than the solution of common salt. Such solvents can be (patent) one or several agents with the pronounced zwitterionic properties (picture of obtaining dimethyl sulfoxide), featured with a polar chart on the electronic acceptor bond of oxygen atom and availability of two electric repellent methyl groups (Photo).

• Topical problem is a study of processes - without destructive extraction of the components from amorphous phase of polysaccharides and determination of diffusion rate of complex solvent and its fractional selectivity is a final objective.

Sol ……time !!!!

Lab (test)

Compositions (flan, Hem, Siln, Wod, …..

FunctionTestLab(“s)

TargetProperties

TASK

(Final plan)

CROPPING

• Thus, for the combined researches on selective diffusion a resorption followed by dehydratation of system is offered — (carrying properties). Such “assistant” in the process of transportation of the dissolved components can be dimethyl formamide. It is necessary to mention the importance of considering the possibility of selective deposition of some agents in the systems under study that can result into creation of unique, natural membranes with radio and photo protecting properties.

Model experiments.• Model experiments were based on

the initial possibility of separating existing formations of supramolecular structures of polysaccharides from the most widely spread fibre-forming plants.

• The most well-known plant for more than 10,000 years is cannabis, cultivated almost in all ecological zones of the world. A considerable contribution to significant facilitation of apprehension of hemp plant capabilities was made by our partner, “Academic Selection Institute of Bast Crops of Ukraine” that fancied a crucially new type of hemp plant with a minimum content of narcotic components. (one can say WITHOUT significant content of narcotic components).

• Due to the researches carried out on model samples it was found out that plasticization effect resulted into additional arrangement of structure providing a possibility for task-oriented change of deformability, and thus, durability of natural cellulose fibres under projected scope of use.

CH3

CH3

S+ – O – + R+

CH3

S+ – OH

CH3

III

• Increase in uniformity of properties makes it possible to suggest that as a result of plasticization the relaxation processes are also followed by the change in the heterolength of chains at the amorphous sections of structure. The study of such properties is a principal trend in the establishment of methods of physical and chemical impact on the modification of structural formations.

• The planned study of the structural dependence and a priori forecast of mechanical characteristics of cellulose fibres and materials produced of, and also their change caused by different factors, seem to be quite difficult. Therefore the calculations both for individual fibres and fibre materials should be included.

• One of the possible lines in physical and chemical modification of the properties can be considered a hydro-pulse, hydrodynamic impact technique.

• This research technique offers a use of fluid phase for the establishment of generic cavitation processes — eigenphase (in general) of mature plants. Or in case of extraction of eigenphase of plants maturation it offers the use of a composite solution facilitating a quick dilution of compounding agents and agglutinants of filament fibres of the plants.

Under further consideration a necessity to carry out dilatometric studies within a wide range of solution concentrations and rates of volumetric changes becomes obvious.

• As a result the kinetics of arrangement of supramolecular structures and their interrelation with amorphous part at a particular life cycle period of development of plant will be examined. We cannot but mention the fact that dilatometric studies are fundamental for this paper. And due to this study in particular, the description of (future) process solutions, crucially new technologies will be obtained. These technological manipulations will start with specification of harvesting moment (or maturation interruption) and refinement, re-thinking of processes of further processing of the plants.

σ 65

50

35

0 0,1 0,2 0,3 0,4 0,5 c

HCOOH

CH3COOH

C3H7COOH

C4H9COOH

G=f(c)

σ =φ(c)

c

G,σ

• This results into development of new innovative trends in cultivation (handling) of plants and creation of new generations of materials with high performance for medicine, motor vehicles, light industry, and so on.

• The application of colloid-chemical principles during development of technology combined with controlled selection of lyophilic colloid formations in the materials followed by the employment of interaction in the processes of redistribution of structural formations in the real plants will make it possible to create fibre materials with predesigned properties

COOH

• To achieve the estimated results the physical techniques are required to be applied with a complete automation system for the phases of information collection, analysis and processing

directly during experiment. As the pattern of changes will require a considerable variation of parameters, for instance, heating or cooling rate.

• For “repacking” a heating technique is usually employed.

• Upon the carried out researches the unique data of the new techniques of modification of supramolecular formations for creation of the best supramolecular packing were obtained. We offer not the heating but the cooling and moreover, an impulse one. In this respect the questions of studying thermodynamics of recrystallization processes arise.

A

B

B

A

Immubilization kit.• This nontrivial phrase was formed spontaneously during

comprehensive consideration of new approaches for management of performance potentials of different structural forms of plant polysaccharides. All possible components contained in a plant during its maturation were taken as the initial ones and all possible forms of their application were considered. Possible options of their separation were then threshed over provided for preservation of functional properties. These properties come often internally into collisions and these collisions help on extraction of these unique substances though along with another, not less important, component. Among many relevant colloid/chemical tools we selected the following — wetting hysteresis, salting out, solubilization, sublimation, lyophilization, reverse osmosis,... Wetting hysteresis we’d rather demonstrate in the figures.

• We offer an interpretation of “PACKING” as some kind of system like “COCOON”, which protects, preserves, creates work environment (ability to carry out functional responsibilities – this includes mustardproof clothing and condoms, and tampons, and so on.

Statement of the problem.• This study, during design of experiment, has the task to develop a research not only in terms

of rational statistics but multidimensional modelling of interrelations between tensor values of stress and system components as well, where the destructions of materials take place, at least plastic deformations occur (a flow state is being set). And these very materials stop following Hook’s law. Already long before destruction a flow property can be observed, large deformation without sensible increase in forces affecting the material. It is interesting that a stress corresponding to occurrence of flow property, further after referred to as tensile strength, appears to be one and the same during testing both for stretching and compression.

• In that case in the course of research it is necessary to rely on representations of viscoplastic and viscoelastic body mechanics.

• The suggested concept and procedure of setting a problem solution transform profoundly the existing patterns, and reconsider and modify age-old practice in this field.

• Theoretical patterns of colloid and chemical formations for lyophilic colloids were taken as the basis for the study of the suggested concept.

• Having chosen as the basis the existing formations of Staudinger, Flory and others, we propose to reconsider the processes of formation of the desired compounds already at the level of colloid lyophilic systems.

• The basic idea is to combine and form the properties with the processes of macromolecule aggregation in polymer solutions, gels and others.

• The similarity of ultimate fibres of cotton and flax stipulated the creation of hypothesis on transformation of the latter into cottonized “flax-like” fibre.

• The need of improvement and development of new technologies is associated with imperfection of equipment for flax preprocessing and with coarsening of flax fibre being observed for the current years. The two-time increase of metric count, increase of diameter of common fibres by 1.3-1.4 times, their hardness, high content of non-cellulose infusions yielded that from total volume of extracted fibre (25-30% of rotted straw weight) for the production of textile goods referred not more than 1/3, the rest of coarse raw material is not fully recalled.

• The techniques of fibre adaptation to the techniques of cotton processing were based on the destruction of adhesive composite of middle lamellas and obtaining a mass of thin ultimate fibres looking like cotton for their processing pursuant to the cotton system of spinning.

• In the making of this idea they tried to ensure the destruction of technical complex of fibre processing by means of chemical breakdown of infusions using mechanical operations. All along with simplicity and allurement of the idea, especially within a lack of raw materials, its implementation requires basically different scientific and design ideas, as the established methods and techniques are not relevant to solving the problems of human population nowadays and in the near future.

• Due to the complexity of spinning process a flax fibre is subject to a number of strict requirements, which can be met only within concurrent development of technologies of mechanical and chemical modifications. Furthermore, rearrangement of processing operation priority in favour of primary importance of colloid and chemical effect at the initial processing phase and this must be already performed immediately during harvesting.

• The offered solutions reduce the whole number of existing complex, energy consuming patterns, environmentally aggressive technologies along with a difficulty of final environmental remediation of such production facilities.

• A reasonable source of raw materials for our technique is the whole range of amorphous and crystalline natural polymeric formations of cellulose.

• LIST of plants:•

• Brief description and possibilities of new technology. New trend and available results.• • The offered process charts are distinguished with contact free

multifactor impact on the raw material using biochemical, physical and chemical effects within the environment of active water solutions, both individual and adopted ones.

• While arranging the impact by means of currents of ionic conduction in local domains combined with electromagnetic radiation, from ultraviolet to infrared and low frequency band — we are able to produce multiple wedging effects during streamer formation, local ebullition of surfaces, forming interphase active hydraulic flows. These active flows are combined with alternating ranges of reversed physical and chemical pressure and create an interphase active tool for controlled variation of output properties, i.e. the properties of the desired permselective or filtering membrane – COCOON.

CH3

CH3

S+ – O – + R+

CH3

S+ – OH

CH3

III

• The listed physical and chemical influencing factors initiate the formation of additional short-living active particles in the form of oxygen ions, ОН-, compounds of НО2, Н2О2, О3 and so on. The occurrence of particles and residuals of certain type can be intensified with electrically active water solutions – anolyte (рН 4-5) and catholyte (рН 12-13).

• During treatment of raw materials in anolyte having oxidation chemical activity, the destruction of pectic substances and tissue lignin take place, followed by bast fibre and wood tissue. The shock waves and cavitation boost this process, ensure wedging out and abstraction of the cracked elements, and they also deliver solution into proximity spacings between fibre bundles (capillary effect). In addition to purification from accessory agents (unnecessary at a given instant), such processing stage provides the basis for ensuring required softness of fibre (if appropriate). Collateral effect of this processing of fibre materials using the offered technique is provided as their thorough asepsis due to bactericidal properties of anolyte, intensified by pulsed electric discharges.

• At the following processing stage of fibre material – in catholyte, having reducing properties and containing a bigger number (than in anolyte) of such compounds as ions of ОН- and hydrogen dioxide, further destruction of lignin and partial bleaching of fibre take place. Under effect of shock waves and cavitation hydrogen dioxide with present ОН- resolves to ions of perhydroxyle of НО2, having higher bleaching properties. Besides, catholyte has higher dissolving, extracting and adsorptive/chemical activity facilitating further purification and separation of large fibre bundles. The result is an achievement of the desired softness, capillarity and degree of fineness (if required).

• Thus, damage to ultimate fibres is excluded (occurs within conventional mechanical techniques of processing) and unique natural properties are preserved, such properties include high strength comparable to the best grades of steel with a degree of fineness similar to natural silk. The technology will make it possible to manufacture products with different features by means of simple change of the designed parameters. On top of everything else — our amorphous phase is filled with fatty acids 3, 6, 9, omega and their content in these cultures is considerable.

• Already evident fields of application:• Simplification of process of extraction from timber of all kinds of cellulose and associated

components; controllability of cellulose fractioning process; obtained possibility of collecting associated fractions of this natural polymer followed by their application; a full range of reclaimed compounds on the basis of sorption and antiseptic properties of the obtained products; impact transfer of medicines from the surface onto the local domains and only for restricted period of effect realization; duplicate unrehearsed effects — possibility to obtain a wide range of natural oil and lubricant additives; gaining a real access to a similar allocation of organic components on the natural silk — cocoon; employment of unique sorption capacities for other types of filling material will provide increase in fire resistance of construction materials; development of new standard packing materials, both for foodstuff and different goods; interest in construction and facing materials for transport industry is predetermined; real techniques of application of shell, peelings, stalks, roots, annual vine prunings appear; substantial increase of raw material output for paper industry (short fibres — 0.5 — 0.7 cm.), from 6-7 % to 87 %; such simplified approach to cellulose production resulted in the following calculation – if a full period of maturation equal to 80—90 days is taken as the basis, and the cellulose yield per hectare is 3.5 (2.5) tonnes, we realize that it is more profitable to collect the stalks of hemp which are left after harvesting the seeds, and by the way they are referred to unaccounted products (in Ukraine), in lieu of growing timber for 25-35 years.

• While summing up the suggested technology it is worth emphasizing the appeared possibility of precise recovery of fancy products and possibility of getting them back into the natural compound, but already for creation of compounds of controlled effect. We are well interested in the long term possibility of technique enhancement on the basis of consideration of the obtained components and their variation as colloid/chemical systems already. The examination of the obtained wide range of new composite materials, such as lyophilic colloids, i.е. multiphase systems will make it possible to develop new ecological materials of selective effect.

• Summary: The technique that was described provides for transfer from toxic, energy-consuming non-organic technology to environmentally compatible multidisciplinary colloid and chemical processes, where it is required to review carefully and distribute the unique products ( by interests).

Stages for implementation of process solutions.

• Stage 1 An indispensible requirement for introduction of the proposed technology is an INSTANT (harvesting time) processing of amorphous (fluid phase) of the plant injection of dissolving systems and active exploration in order to evolve the process of dissolution of the whole amorphous phase, it refers to ALL cellulose forming plants and their peeling (shell).

• Stage 2 Extraction and fractionation of a fluid phase into component parts and their conservation for further testing.

• Stage 3 Injection of bioactive, surface active, ion active solvents into the remaining matrix of polysaccharides. Activation of solubilization and salting out processes, i.e. formation simplification for lyophilic colloids in the modes of isochoric change of temperature parameters and vice versa, change of pressure during isothermal adsorption.

• Stage 4 Fractionation of the separated fluid phase (distillation) into functional components, their encapsulation. (fatty acids, binding, germicidal, bioactive, sorption, other properties) for preservation of the exclusive functional properties.

• Stage 5 Injection of the prepared fluid phase (with the necessary selection of properties) into matrix cellulose and its fixing in the created compound under temperature modes and properties as applied to the conditions of future functional working space.

• Stage 6 Development of the most efficient options of the created compounds, obligatory pursuance of the kinetics of structural formation during biosynthesis of basic plant source for polymer formations. Volumetric dilatometry together with implementation of control of the natural processes of recrystallization and structure formation during alternating thermal rates of system formation. OBJECTIVE – determination of the most rational stopping time for the natural process of structure formation.

• Stage 7 Empiric exploration of the required data will make it possible to reflect visually the multifactor processes for the purpose of determination of the most efficient parameters for acquisition of the desired product (medicine, cord, packing).

• Stage 8 Creation of test samples. Testing of the obtained samples (cotton wool, sorbing agents, germicidal materials, ...) in medical institutions, (woven, non-woven textile, construction textile …) in sports industry, (water absorbing textile, barrier textile, conservation textile, filtering textile…) in agriculture industry having one common objective – Not to produce more but to Save more. (membrane textile with active nutritional functions) food industry – DRYGALO and the like, i.e. realization of the emerging possibilities in creation of food products of extended storage, without implementation of deep freezing stage.

• Stage 9 Development of guidelines for commercial implementation of the

developed techniques for the desired physical and chemical colloid systems.

List of partners ready to take part in the implementation of certain stages.

• Kiev National University of Technology and Design (textile technologies, winner of Ukrainian state award for the development of textile technologies)

• Kiev State University (determination of cristallinity, surfaces, study of surface properties)

• Academic Institute of Biochemistry and Petrochemistry.• Academy of Agriculture with its network of Institutes of Selection.• Askania-Nova biosphere reserve• Ukrshovk Corporation. (corporation for Ukrainian silk).• Private Scientific and Research Company “Applied technologies and design” • The report in candidacy for organization of the collaborative research

topic is submitted by: Dr.(Chemistry of materials )., assistant professor O.V. Anokhin, Dr. of

physical – chemistry (Engineering) Professor T.S. Shostak Kiev National University of Technologies and Design. Information and Management Division.