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The drift time spectra of polycyclic aromatic hydrocarbons (PAH), alkylbenzenes and alkylphenylethers were recorded with a laser-based ion mobility (IM) spectrometer. The ion mobilities of all compounds were determined in helium as drift gas. This allows the calculation of the diffusion cross sections (Omegacalc) on the basis of the exact hard sphere scattering model (EHSSM) and their comparison with the experimentally determined diffusion cross sections (Omegaexp). These Omegaexp/Omegacalc-correlations are presented for molecules with a rigid structure like PAH and prove the reliability of the theoretical model and experimental method. The increase of the selectivity of IM spectrometry is demonstrated using resonance enhanced multiphoton ionisation (REMPI) at atmospheric pressure, realized by tuneable lasers. The REMPI spectra of nine alkylbenzenes and alkylphenylethers are investigated. On the basis of these spectra, the complete qualitative distinction of eight compounds in a mixture is shown. These experiments are extended to alkylbenzene isomer mixtures.
The performance of a home-built tunable diode laser (TDL) spectrometer has been optimized regarding multi-line detection of carbon dioxide in natural gases. In the regime of the (30<SUP>0</SUP>1)<SUB>III</SUB> ← (000) band of <SUP>12</SUP>CO<SUB>2</SUB> around 1.6 μm, the dominating isotope species <SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, and <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O were detected simultaneously. In contrast to most established techniques, selective measurements are performed without any sample preparation. This is possible since the CO<SUB>2</SUB> detection is free of interference from water, ubiquitous in natural gases. Detection limits in the range of a few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. Linear calibration plots cover a dynamic range of four orders of magnitude, allowing for quantitative CO<SUB>2</SUB> detection in various samples, like soil and breath gas. High isotopic resolution enables the excellent selectivity, sensitivity, and stability of the chosen analytical concept. The obtained isotopic resolution of typically ± 1.0 ‰ and ± 1.5 ‰ (for 3 vol. % and 0.7 vol. % of CO<SUB>2</SUB>, respectively) offers a promising analytical tool for isotope-ratio determination of carbon dioxide in soil gas. Preliminary experiments on soil respiration for the first time combine the on-line quantification of the overall carbon dioxide content with an optode sensor and isotopic determination (TDL system) of natural gas species.
The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (30<SUP>0</SUP>1)<SUB>III</SUB> / (000) band of <SUP>12</SUP>CO<SUB>2</SUB> around 1.6 μm, the dominating isotope species <SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, and <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision —typically ±1‰ and ±6‰ for 3% and 0.7% of CO<SUB>2</SUB>, respectively— renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate <SUP>12</SUP>CO<SUB>2</SUB> line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.
The goal of this work was to study the binding of ions to polymers and lipid bilayer membranes in aqueous solutions. In the first part of this work, the influence of various inorganic salts and polyelectrolytes on the structure of water was studied using Isothermal Titration Calorimetry (ITC). The heat of dilution of the salts was used as a scale of water structure making and breaking of the ions. The heats of dilution could be attributed to the Hofmeister Series. Following this, the binding of Ca2+ to poly(sodium acrylate) (NaPAA) was studied. ITC and a Ca2+ Ion Selective Electrode were used to measure the reaction enthalpy and binding isotherm. Binding of Ca2+ ions to PAA, was found to be highly endothermic and therefore solely driven by entropy. We then compared the binding of ions to the one-dimensional PAA polymer chain to the binding to lipid vesicles with the same functional groups. As for the polymer, Ca2+ binding was found to be endothermic. Binding of calcium to the lipid bilayer was found to be weaker than to the polymer. In the context of these experiments, it was shown that Ca2+ not only binds to charged but also to zwitterionic lipid vesicles. Finally, we studied the interaction of two salts, KCl and NaCl, to a neutral polymer gel, PNIPAAM, and to the ionic polymer PAA. Combining calorimetry and a potassium selective electrode we observed that the ions interact with both polymers, whether containing charges or not.
Nanostructured materials are the materials having structural features on the scale of nanometers i.e. 10-9 m. the structural features can enhance the natural properties of the materials or induce additional properties, which are useful for day to technology as well as the future technologies One way to synthesize nanostructured materials is using templating techniques. The templating process involves use of a certain “mould” or “scaffold” to generate the structure. The mould is called as the template, can be a single molecule or assembly of molecule or a larger object, which has its own structure. The product material can be obtained by filling the space around the template with a “precursor”, transformation of precursor into the desired material and then removal of template to get product. The precursor can be any chemical moiety that can be easily transformed in to the desired material. Alternatively the desired material is processed into very tiny bricks or “nano building blocks (NBB)” and the product is obtained by arrangement of the NBB by using a scaffold. We synthesized porous metal oxide spheres of namely TiO2-M2O3: titanium dioxide- M-oxide (M = aluminum, gallium and indium) TiO2-M2O3 and cerium oxide-zirconium oxide solid solution. We used porous polymeric beads as templates. These beads used for chromatographic purposes. For the synthesis of TiO2-M2O3 we used metal- alkoxides as precursor. The pore of beads were filled with precursor and then reacted with water to give transformation of the precursor to amorphous oxide network. The network is crystallized and template is removed by heat treatment at high temperatures. In a similar way we obtained porous spheres of CexZr1-xO2. For this we synthesized nanoparticle of CexZr1-xO2 and used then for the templating process to obtain porous CexZr1-xO2 spheres. Additionally, using the same nanoparticles we synthesized nano-porous powder using self-assembly process between a block-copolymers scaffold and nanoparticles. Morphological and physico-chemical properties of these materials were studies systematically by using various analytical techniques TiO2-M2O3 material were tested for photocatalytic degradation of 2-Chlorophenol a poisonous pollutant. While CexZr1-xO2 spheres were tested for methanol steam reforming reaction to generate hydrogen, which is a fuel for future generation power sources like fuel cells. All the materials showed good catalytic performance.
Combining the magnetic properties of a given material with the tremendous advantages of colloids can exponentially increase the advantages of both systems. This thesis deals with the field of magnetic nanotechnology. Thus, the design and characterization of new magnetic colloids with fascinating properties compared with the bulk materials is presented. Ferrofluids are referred to either as water or organic stable dispersions of superparamagnetic nanoparticles which respond to the application of an external magnetic field but lose their magnetization in the absence of a magnetic field. In the first part of this thesis, a three-step synthesis for the fabrication of a novel water-based ferrofluid is presented. The encapsulation of high amounts of magnetite into polystyrene particles can efficiently be achieved by a new process including two miniemulsion processes. The ferrofluids consist of novel magnetite polystyrene nanoparticles dispersed in water which are obtained by three-step process including coprecipitation of magnetite, its hydrophobization and further surfactant coating to enable the redispersion in water and the posterior encapsulation into polystyrene by miniemulsion polymerization. It is a desire to take advantage of a potential thermodynamic control for the design of nanoparticles, and the concept of "nanoreactors" where the essential ingredients for the formation of the nanoparticles are already in the beginning. The formulation and application of polymer particles and hybrid particles composed of polymeric and magnetic material is of high interest for biomedical applications. Ferrofluids can for instance be used in medicine for cancer therapy and magnetic resonance imaging. Superparamagnetic or paramagnetic colloids containing iron or gadolinium are also used as magnetic resonance imaging contrast agent, for example as a important tool in the diagnosis of cancer, since they enhance the relaxation of the water of the neighbouring zones. New nanostructured composites by the thermal decomposition of iron pentacarbonyl in the monomer phase and thereafter the formation of paramagnetic nanocomposites by miniemulsion polymerization are discussed in the second part of this thesis. In order to obtain the confined paramagnetic nanocomposites a two-step process was used. In the first step, the thermal decomposition of the iron pentacarbonyl was obtained in the monomer phase using oleic acid as stabilizer. In the second step, this iron-containing monomer dispersion was used for making a miniemulsion polymerization thereof. The addition of lanthanide complexes to ester-containing monomers such as butyl acrylate and subsequent polymerization leading to the spontaneous formation of highly organized layered nanocomposites is presented in the final part of this thesis. By an one-step miniemulsion process, the formation of a lamellar structure within the polymer nanoparticles is achieved. The magnetization and the NMR relaxation measurements have shown these new layered nanocomposites to be very apt for application as contrast agent in magnetic resonance imaging.
During the past several decades polymer materials become widely used as components of medical devices and implants such as hemodialysers, bioartificial organs as well as vascular and recombinant surgery. Most of the devices cannot avoid the blood contact in their use. When the polymer materials come in contact with blood they can cause different undesired host responses like thrombosis, inflammatory reactions and infections. Thus the materials must be hemocompatible in order to minimize these undesired body responses. The earliest and one of the main problems in the use of blood-contacting biomaterials is the surface induced thrombosis. The sequence of the thrombus formation on the artificial surfaces has been well established. The first event, which occurs, after exposure of biomaterials to blood, is the adsorption of blood proteins. Surface physicochemical properties of the materials as wettability greatly influence the amount and conformational changes of adsorbed proteins. In turn the type, amount and conformational state of the adsorbed protein layer determines whether platelets will adhere and become activated or not on the artificial surface and thus to complete the thrombus formation. The adsorption of fibrinogen (FNG), which is present in plasma, has been shown to be closely related to surface induced thrombosis by participating in all processes of the thrombus formation such as fibrin formation, platelet adhesion and aggregation. Therefore study the FNG adsorption to artificial surfaces could contribute to better understanding of the mechanisms of platelet adhesion and activation and thus to controlling the surface induced thrombosis. Endothelization of the polymer surfaces is one of the strategies for improving the materials hemocompatibility, which is believed to be the most ideal solution for making truly blood-compatible materials. Since at physiological conditions proteins such as FNG and fibronectin (FN) are the usual extracellular matrix (ECM) for endothelial cells (EC) adhesion, precoating of the materials with these proteins has been shown to improve EC adhesion and growth in vitro. ECM proteins play an essential role not only like a structural support for cell adhesion and spreading, but also they are important factor in transmitting signals for different cell functions. The ability of cells to remodel plasma proteins such as FNG and FN in matrix-like structures together with the classical cell parameters such as actin cytoskeleton and focal adhesion formation could be used as an criteria for proper cell functioning. The establishment and the maintaining of delicate balance between cell-cell and cell-substrate contacts is another important factor for better EC colonization of the implants. The functionality of newly established endothelium in order to produce antithromotic substances should be always considered when EC seeding is used for improving the hemocompatibility of the polymer materials. Controlling the polymer surface properties such as surface wettability represents a versatile approach to manipulate the above cellular responses and therefore can be used in biomaterial and tissue engineering applications for producing better hemocompatible materials.
Results of an inter-laboratory round-robin study of the application of time-resolved emission spectroscopy (TRES) to the speciation of uranium(VI) in aqueous media are presented. The round-robin study involved 13 independent laboratories, using various instrumentation and data analysis methods. Samples were prepared based on appropriate speciation diagrams and, in general, were found to be chemically stable for at least six months. Four different types of aqueous uranyl solutions were studied: (1) acidic medium where UO22+aq is the single emitting species, (2) uranyl in the presence of fluoride ions, (3) uranyl in the presence of sulfate ions, and (4) uranyl in aqueous solutions at different pH, promoting the formation of hydrolyzed species. Results between the laboratories are compared in terms of the number of decay components, luminescence lifetimes, and spectral band positions. The successes and limitations of TRES in uranyl analysis and speciation in aqueous solutions are discussed.
The present work is dealing with the first synthesis and characterisation of amphiphilic diblock copolymers bearing b-dicarbonyl (acetoacetoxy) chelating residues. Polymers were obtained by Group Transfer Polymerisation (GTP)/acetoacetylation and controlled radical polymerisation techniques (RAFT).Different micellar morphologies of poly(n-butyl methacrylate)-block-poly[2-(acetoacetoxy)ethyl methacrylate] (pBuMA-b-pAEMA) were observed in cyclohexane as a selective solvent. Depending on the block length ratio, either spherical, elliptical, or cylindrical micelles were formed. The density of the polymer chains at the core/corona interface is considerably higher as compared to any other strongly segregating system reported in the literature. It is demonstrated that there are H-bond interactions existing between acetoacetoxy groups, which increase the incompatibility between block segments. In addition, such interactions lead to the formation of secondary structures (such as b-sheets or globular structures) and larger superstructures in the micrometer length scale.Block copolymers were also used to solubilise metal ion salts of different geometries and oxidation states in organic media, in which are otherwise insoluble. Sterically stabilised colloidal hybrid materials are formed, i.e. monodisperse micelles having the metal ion salt incorporated in their core upon complexation with the ligating pAEMA block, whereas pBuMA forms the solvating corona responsible for stabilisation in solution. Systematic studies show that the aggregation behaviour is dependent on different factors, such as the tautomeric form of the beta-dicarbonyl ligand (keto/enol) as well as the nature and amount of added metal ion salt.
The colloidal systems are present everywhere in many varieties such as emulsions (liquid droplets dispersed in liquid), aerosols (liquid dispersed in gas), foam (gas in liquid), etc. Among several new methods for the preparation of colloids, the so-called miniemulsion technique has been shown to be one of the most promising. Miniemulsions are defined as stable emulsions consisting of droplets with a size of 50-500 nm by shearing a system containing oil, water, a surfactant, and a highly water insoluble compound, the so-called hydrophobe 1. In the first part of this work, dynamic crystallization and melting experiments are described which were performed in small, stable and narrowly distributed nanodroplets (confined systems) of miniemulsions. Both regular and inverse systems were examined, characterizing, first, the crystallization of hexadecane, secondly, the crystallization of ice. It was shown for both cases that the temperature of crystallization in such droplets is significantly decreased (or the required undercooling is increased) as compared to the bulk material. This was attributed to a very effective suppression of heterogeneous nucleation. It was also found that the required undercooling depends on the nanodroplet size: with decreasing droplet size the undercooling increases. 2. It is shown that the temperature of crystallization of other n-alkanes in nanodroplets is also significantly decreased as compared to the bulk material due to a very effective suppression of heterogeneous nucleation. A very different behavior was detected between odd and even alkanes. In even alkanes, the confinement in small droplets changes the crystal structure from a triclinic (as seen in bulk) to an orthorhombic structure, which is attributed to finite size effects inside the droplets. An intermediate metastable rotator phase is of less relevance for the miniemulsion droplets than in the bulk. For odd alkanes, only a strong temperature shift compared to the bulk system is observed, but no structure change. A triclinic structure is formed both in bulk and in miniemulsion droplets. 3. In the next part of the thesis it is shown how miniemulsions could be successfully applied in the development of materials with potential application in pharmaceutical and medical fields. The production of cross-linked gelatin nanoparticles is feasible. Starting from an inverse miniemulsion, the softness of the particles can be controlled by varying the initial concentration, amount of cross-link agent, time of cross-linking, among other parameters. Such particles show a thermo-reversible effect, e.g. the particles swell in water above 37 °C and shrink below this temperature. Above 37 °C the chains loose the physical cross-linking, however the particles do not loose their integrity, because of the chemical cross-linking. Those particles have potential use as drug carriers, since gelatin is a natural polymer derived from collagen. 4. The cross-linked gelatin nanoparticles have been used for the biomineralization of hydroxyapatite (HAP), a biomineral, which is the major constituent of our bones. The biomineralization of HAP crystals within the gelatin nanoparticles results in a hybrid material, which has potential use as a bone repair material. 5. In the last part of this work we have shown that layers of conjugated semiconducting polymers can be deposited from aqueous dispersion prepared by the miniemulsion process. Dispersions of particles of different conjugated semiconducting polymers such as a ladder-type poly(para-phenylene) and several soluble derivatives of polyfluorene could be prepared with well-controlled particle sizes ranging between 70 - 250 nm. Layers of polymer blends were prepared with controlled lateral dimensions of phase separation on sub-micrometer scales, utilizing either a mixture of single component nanoparticles or nanoparticles containing two polymers. From the results of energy transfer it is demonstrated that blending two polymers in the same particle leads to a higher efficiency due to the better contact between the polymers. Such an effect is of great interest for the fabrication of opto-electronic devices such as light emitting diodes with nanometer size emitting points and solar cells comprising of blends of electron donating and electron accepting polymers.
Investigations with frequency domain photon density waves allow elucidation of absorption and scattering properties of turbid media. The temporal and spatial propagation of intensity modulated light with frequencies up to more than 1 GHz can be described by the P1 approximation to the Boltzmann transport equation. In this study, we establish requirements for the appropriate choice of turbid model media and characterize mixtures of isosulfan blue as absorber and polystyrene beads as scatterer. For these model media, the independent determination of absorption and reduced scattering coefficients over large absorber and scatterer concentration ranges is demonstrated with a frequency domain photon density wave spectrometer employing intensity and phase measurements at various modulation frequencies.
Steady-state and time-resolved fluorescence methods were applied to investigate the fluorescence properties of humic substances of different origins. Using standard 2D emission and total luminescence spectra, fluorescence maxima, the width of the fluorescence band and a relative fluorescence quantum efficiency were determined. Different trends for fulvic acids and humic acids were observed indicating differences in the heterogeneity of the sample fractions. The complexity of the fluorescence decay of humic substances is discussed and compared to simple model compounds. The effect of oxidation of humic substances on their fluorescence properties is discussed as well.
In the present study, photophysical properties of [N]phenylenes were studied by means of stationary and time-resolved absorption and fluorescence spectroscopy (in THF at room temperature). For biphenylene (1) and linear [3]phenylene (2a), internal conversion (IC) with quantum yields ΦIC > 0.99 is by far the dominant mechanism of S1 state deactivation. Angular [3]phenylene (3a), the zig-zag [4]- and [5]phenylenes (3b), (3c), and the triangular [4]phenylene (4) show fluorescence emission with fluorescence quantum yieds and lifetimes between ΦF = 0.07 for (3a) and 0.21 for (3c) and τF = 20 ns for (3a) and 81 ns for (4). Also, compounds (3) and (4) exhibit triplet formation upon photoexcitation with quantum yields as high as ΦISC = 0.45 for (3c). The strong differences in the fluorescence properties and in the triplet fromation efficiencies between (1) and (2a) on one hand and (3) and (4) on the other are related to the remarkable variation of the internal conversion (IC) rate constants kIC. A tentative classification of (1) and (2a) as “fast IC compounds”, with kIC > 109 s-1, and of (3) and (4) as “slow IC compounds”, with kIC ≈ 107 s-1, is suggested. This classification cannot simply be related to Hückel’s rule-type concepts of aromaticity, because the group of “fast IC compounds” consists of “antiaromatic” (1) and “aromatic” (2a), and the group of “slow IC compounds” consists of “antiaromatic” (3b), (4) and “aromatic” (3a), (3c). The IC in the [N]phenylenes is discussed within the framework of the so-called energy gap law established for non-radiative processes in benzenoid hydrocarbons.
An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert–Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 °C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7–9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene–arene, and fluorine–π interactions.
Research on monolayers of amphiphilic lipids on aqueous solution is of basic importance in surface science. Due to the applicability of a variety of surface sensitive techniques, floating insoluble monolayers are very suitable model systems for the study of order, structure formation and material transport in two dimensions or the interactions of molecules at the interface with ions or molecules in the bulk (headword 'molecular recognition'). From the behavior of monolayers conclusions can be drawn on the properties of lipid layers on solid substrates or in biological membranes. This work deals with specific and fundamental interactions in monolayers both on the molecular and on the microscopic scale and with their relation to the lattice structure, morphology and thermodynamic behavior of monolayers at the air-water interface. As model system especially monolayers of long chain fatty acids are used, since there the molecular interactions can be gradually adjusted by varying the degree of dissociation by means of the suphase pH value. For manipulating the molecular interactions besides the subphase composition also temperature and monolayer composition are systematically varied. The change in the monolayer properties as a function of an external parameter is analyzed by means of isotherm and surface potential measurements, Brewster-angle microscopy, X-ray diffraction at grazing incidence and polarization modulated infrared reflection absorption spectroscopy. For this a quantitative measure for the molecular interactions and for the chain conformational order is derived from the X-ray data. The most interesting results of this work are the elucidation of the origin of regular polygonal and dendritic domain shapes, the various effects of cholesterol on molecular packing and lattice order of long chain amphiphiles, as well as the detection of an abrupt change in the head group bonding interactions, the chain conformational order and the phase transition pressure between tilted phases in fatty acid monolayers near pH 9. For the interpretation of the latter point a model of the head group bonding structure in fatty acid monolayers as a function of the pH value is developed.
Contents: Production and Applications of Chitin and Chitosan Krill as a promising raw material for the production of chitin in Europe - Containerized plant for producing chitin - Preparation and characterization of chitosan from Mucorales - Chitosan from Absidia orchidis - Scaling up of lactic acid fermentation of prawn wastes in packed-bed column reactor for chitin recovery - Preparation of chitin by acetic acid fermentation - Inter-source reproducibility of the chitin deacetylation process - Comparative analysis of chitosans from insects and crustacea - Effect of the rate of deacetylation on the physico-chemical properties of cuttlefish chitosan - Deacetylation of chitin by fungal enzymes - Production of partially degraded chitosan with desired molecular weight - Chitin-containing materials Mycoton for wounds treatment - Biological activity of selected forms of chitosan - Application of chitosan on the preservation quality of cut flowers - Preparation and characterization of chitosan films: application in cell cultures - Transport phenomena in chitin gels - Symplex membranes of chitosan and sulphoethylcellulose - Preparation and use of chitosan-Ca pectinate pellets - Bioseparation of protein from cheese whey by using chitosan coagulation and ultrafiltration membranes - Preparation of silk fibroin/chitosan fiber - Preparation of paper sheets containing microcrystalline chitosan - Applications of chitosan in textile printing - Permanent modification of fibrous materials with biopolymers - Ion exchanger from chitosan - Chitosan in waste water treatment - The immobilization of tyrosinase on chitin and chitosan and its possible use in wastewater treatment - Utilization of modified chitosan in aqueous system treatment Biomaterials Chemical and preclinical studies on 6-oxychitin - Diverse biological effects of fungal chitin-glucan complex - Effect of concentration of neutralizing agent on chitosan membrane properties - Preliminary investigation of the compatibility of a chitosan-based peritoneal dialysis solution - Influence of chitosan on the growth of several cellular lines - A new chitosan containing phosphonic group with chelating properties - Biocompatibility of chitin materials using cell culture method Oral Administration of Chitosan Recent results in the oral administration of chitosan - Reduction of absorption of dietary lipids and cholesterol by chitosan, its derivatives and special formulations - Chitosan in weight reduction: results from a large scale consumer study - Conformation of chitosan ascorbic acid salt - Trimethylated chitosans as safe absorption enhancers for transmucosal delivery of peptide drugs - Chitosan derivates as intestinal penetration enhancers of the peptide drug buserelin in vivo and in vitro - Chitosan microparticles for oral vaccination: optimization and characterization - Effect of chitosan in enhancing drug delivery across buccal mucosa - Influence of chitosans on permeability of human intestinal epithelial (Caco-2) cells: The effect of molecular weight, degree of deacetylation and exposure time - Oral polymeric N-acetyl-D-glucosamine as potential treatment for patients with osteoarthritis - Clinicoimmunological efficiency of the chitin-containing drug Mycoton in complex treatment of a chronic hepatitis - Interactions of chitin, chitosan, N-laurylchitosan, and N-dimethylaminopropyl chitosan with olive oil - The chitin-containing preparation Mycoton in a pediatric gastroenterology case - Antifungal activity and release behaviour of cross-linked chitosan films incorporated with chlorhexidine gluconate - Release of N-acetyl-D-glucosamine from chitosan in saliva - Physical and Physicochemical Properties Recent approach of metal binding by chitosan and derivatives - As(V) sorption on molybdate-impregnated chitosan gel beads (MICB) - Influence of medium pH on the biosorption of heavy metals by chitin-containing sorbent Mycoton - Comparative studies on molecular chain parameters of polyelectrolyte chains: the stiffness parameter B and temperature coefficient of intrinsic viscosity of chitosans and poly(diallyldimethylammonium chloride) - Crystalline behavior of chitosan - The relationship between the crystallinity and degree of deacetylation of chitin from crab shell - Reversible water-swellable chitin gel: modulation of swellability - Syneresis aspects of chitosan based gel systems - In situ chitosan gelation using the enzyme tyrosinase - Preparation and characterization of controlling pore size chitosan membranes - Fabrication of porous chitin matrices - Changes of polydispersity and limited molecular weight of ultrasonic treated chitosan - A statistical evaluation of IR spectroscopic methods to determine the degree of acetylation of ?-chitin and chitosan - Products of alkaline hydrolysis of dibutyrylchitin: chemical composition and DSC investigation - Chitosan emulsification properties Chemistry of Chitin and Chitosan Chemically modified chitinous materials: preparation and properties - Progress on the modification of chitosan - The graft copolymerization of chitosan with methyl acrylate using an organohalide-manganese carbonyl coinitiator system - Grafting of 4-vinylpyridine, maleic acid and maleic anhydride onto chitin and chitosan - Peptide synthesis on chitosan/chitin - Graft copolymerization of methyl methacrylate onto mercapto-chitin - Thermal depolymerization of chitosan salts - Radiolysis and sonolysis of chitosan - two convenient techniques for a controlled reduction of molecular weight - Thermal and UV degradation of chitosan - Heat-induced physicochemical changes in highly deacetylated chitosan - Chitosan fiber and its chemical N-modification at the fiber state for use as functional materials - Preparation of a fiber reactive chitosan derivative with enhanced microbial activity - Chromatographic separation of rare earths with complexane types of chemically modified chitosan - The effects of detergents on chitosan - Chitosan-alginate PEC films prepared from chitosan of different molecular weights - Enzymology of Chitin and Chitosan Biosynthesis and Degradation Enzymes of chitin metabolism for the design of antifungals - Enzymatic degradation of chitin by microorganisms - Kinetic behaviours of chitinase isozymes - An acidic chitinase from gizzards of broiler (Gallus gallus L.) - On the contribution of conserved acidic residues to catalytic activity of chitinase B from Serratia marcescens - Detection, isolation and preliminary characterisation of a new hyperthermophilic chitinase from the anaerobic archaebacterium Thermococcus chitonophagus - Biochemical and genetic engineering studies on chitinase A from Serratia marcescens - Induction of chitinase production by Serratia marcescens, using a synthetic N-acetylglucosamine derivative - Libraries of chito-oligosaccharides of mixed acetylation patterns and their interactions with chitinases - Approaches towards the design of new chitinase inhibitors - Allosamidin inhibits the fragmentation and autolysis of Penicillium chrysogenum - cDNA encoding chitinase in the midge, Chironomus tentans - Extraction and purification of chitosanase from Bacillus cereus - Substrate binding mechanism of chitosanase from Streptomyces sp. N174 - Chitosanase-catalyzed hydrolysis of 4-methylumbelliferyl ?-chitotrioside - A rust fungus turns chitin into chitosan upon plant tissue colonization to evade recognition by the host - Antibiotic kanosamine is an inhibitor of chitin biosynthesis in fungi - PCR amplification of chitin deacetylase genes - Amplification of antifungal effect of GlcN-6-P synthase and chitin synthase inhibitors - ?-N-Acetylhexosaminidases: two enzyme families, two mechanisms - Purification and characterisation of chitin deacetylase from Absidia orchidis - Effect of aluminium ion on hydrolysis reaction of carboxymethyl- and dihydroxypropyl-chitin with lysozyme - Structure and function relatioship of human N-acetyl-D-glucosamine 2-epimerase (renin binding protein) - Identification of active site residue(s)
Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles.
A series of amphiphilic copolymers is prepared by copolymerization of choline methacrylate with 1,1,2,2-tetrahydroperfluorooctyl methacrylate in varying amounts. The copolymers bearing fluorocarbon chains are studied concerning their effects on viscosity, solubilization and surface activity in aqueous solution, exhibiting a general behavior characteristic for polysoaps. The results are compared with the ones obtained for an analogous series of amphiphilic copolymers bearing hydrocarbon chains.
The article reviews water-soluble polymers characterized by surfactant side chains, and related amphiphilic polymers. Various synthetic approaches are presented, and rules for useful molecular architectures are given. Models for the self-organization of such polymers in water are presented comparing them with the micellization of low molecular weight surfactants. Highlighting key properties of aqueous polysoap solutions such as viscosity, surface tension and solubilization power, some structure-property relationships are established. Further, the formation of mesophases and of superstructures in bulk is addressed. Finally, the functionalization of polysoaps, and potential applications are discussed.
Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly{3 [N(-methacryloyloxyalkyl)] N, [N-dimethylammonio propanesulfonate] with sodium iodide in the frequency range of 10²Hz-10(up)7 Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arrhenius-like temperature depence with activation energy EA = 47 KJ/mol, this relaxation process is assigned to fluctuation of the quaternary ammonium groups in the side chains. At higher temperatures, the dielectric properties and the conductivity are primarily dominated by the mobile inorganic ions: conductivity strongly depends on the salt concentration, showing a pronounced electrode polarization effect. The frequency and salt concentration, dependences of the conductivity can be quantitatively described as hopping of charge carriers being subject to spatially randomly varying energy barriers. For the low-frequency regime and for the critical frequency marking the onset of the conductivity's dispersion, the Barton-Nakajima-Namikawa (BNN) relationship is fulfilled.
The prepaparation of amorphous, homogeneous blends of zwitterionic polymers and transition metal salts was investigated. Homogeneous miscibility was achieved in many cases up to equimolar amounts of salt, depending on the anion and cation chosen. Various analytical techniques point to a solid state solution of the inorganic ions in the polymer matrix.
Solubilization by polysoaps
(1994)
The aqueous solubilization power of several series of micellar homopolymers and copolymers (polysoaps) is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect ot the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes.
Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a main-chain spacer model proposed recently. All water-soluble polymers exhibit characteristic features of classical polysoaps, as shown by surface tension measurements and by solubilization of hydrophobic dyes. In contrast, the water-insoluble copolymers are capable to form stable monolayers at the air-water interface.
This article describes recent achievements in the field of micellar polymers, or polysoaps. Taking advantage of zwitterionic model polymers, systematic variations of the molecular architecture have provided an improved understanding of the relationship between the molecular structure of the polymers and their key properties such as surface activity and solubilization capacity. Useful rules are established, which take into account much of the previous data in the literature.
A set of novel zwitterionic side-chain polyacrylates and polymethacrylates is studied by X-ray scattering. The structural order both in the short-range and long-range scale is investigated. The influence of the polymer backbone, of different locations of the ionic groups in isomeric polymers, of bound water and of added inorganic salts on the bulk structures is studied, and the observed rearrangements are analysed.
4-Phenylphenoxazinones were isolated after biomimetic oxidation, using diphenoloxidases of insect cuticle, mushroom tyrosinase, or after autoxidation of N-acetyldopamine (Image ) in the presence of β-alanine, β-alanine methyl ester or N-acetyl-L-lysine. They are formed presumably by addition of 2-aminoalkyl-5-alkylphenols to the o-quinone of biphenyltetrol which, in turn, arises from oxidative coupling of. The structures of present the first examples for the assembly of reasonably stable intermediates in the rather complex process of chemical modifications of aliphatic amino acid residues by o-quinones.
Mixed monolayers and Langmuir-Blodgett multilayers of functional low molecular weight guest compounds, especially nonlinear optical (NLO) dyes, within the matrix of an amphotropic spacer polymer have been prepared. The polymer matrix enabled the transfer of guest compounds not capable of self-organizing at the air-water interface by themselves. The structure of the LB multilayers and the transfer process were studied by small angle X-ray scattering and UV-visible spectroscopy. Good NLO coefficients were found in the mixed films.
Several types of insect cuticle contain enzymes catalyzing the formation ofof adducts between N-acetyldopamine (NADA) and N-acetylhistidine (NAH). Two such adducts, NAH-NADA-I and NAH NADA-II, have been isolated and their structures determined. In one of the adducts the link connecting the two residues occurs between the I-position (ß-position) in the NADA side chain and the 1-N atom (τ-N) in the imidazole ring of histidine. Diphenoloxidase activity alone is not sufficient for formation of this adduct, whereas extracts containing both diphenoloxidase and o-quinone-p-quinone methide isomerase activities catalyze the coupling reaction. The adduct consists of a mixture of two diastereomers and they are presumably formed by spontaneous reaction between enzymatically produced NADA-p-quinone methide and N-acetylhistidine. The other adduct has been identified as a ring addition product of N-acetylhistidine and NADA. In contrast to the former adduct it can be formed by incubation of the two substrates with mushroom tyrosinase alone. An adduct between N-acetylhistidine and the benzodioxan-type NADA-dimer is produced in vitro, when the N-acetylhistidine-NADA adduct is incubated with NADA and locust cuticle containing a 1,2-dehydro-NADA generating enzyme system. Trimeric NADA-polymerization products of the substituted benzodioxan-type have been obtained from in vivo sclerotized locust cuticle, confirming the ability of cuticle to produce NADA-oligomers. The results indicate that some insect cuticles contain enzymes promoting linkage of oxidized NADA to histidine residues. It is suggested that histidine residues in the cuticular proteins can serve as acceptors for oxidized NADA and that further addition of NADA-residues to the phenolic groups of bound NADA can occur, resulting in formation of protein-linked NADA-oligomers. The coupling reactions identified may be an important step in natural cuticular sclerotization.
The molecular packing and spatial correlations of two isomeric zwitterionic polymethacrylates and one polyacrylate analog are studied by means of X-ray analysis and conformational calculations. The analysis of the correlation functions and density distribution profiles suggest a double-layered molecular packing which is discussed for the three polymers investigated, with respect to their different chemical structures. Whereas the zwitterionic polymethacrylates studied exhibit liquid-like short-range order, the polyacrylate analog exhibits an ordered double-layered superstructure.
The use of preformed polymers for the preparation of Langmuir-Blodgett (LB) multilayers is reviewed. Principles for polymer self-organization are outlined and the appropriate molecular designs are discussed. Recent developments in the different classes of polymers for LB multilayers are presented, and their outstanding properties highlighted.
Cationic and zwitterionic polymerizable surfactants bearing tri- and tetraethyleneglycol spacer groups between the polymerizable moiety and the surfactant structure were prepared and polymerized. Monomers and polymers were investigated with respect to their aggregation behavior in aqueous systems and compared to analogous monomers and polymers lacking spacer groups. In the case of the monomeric surfactants, the spacer groups depress both the Kraffttemperature and the critical micelle concentration. the area occupied per molecule at the air-water interface is substantially enlarged by the spacers, whereas the depression of surface tension is nearly constant. Although the monomers with and without spacers are true surfactants, all the polymers are water-insoluble, but form monomolecular layers at the air-water interface. In analogy to the monomer behavior, the incorporation of the spacer groups increases the area occupied per repeat unit at the air-water interface substantially, but hardly affects the surface activity.
Aus dem Inhalt: Melanins are complex polyphenolic polymers. They are usually formed in nature by enzyme-catalyzed oxidative polymerization of o-diphenols. The deep black eumelanins, derived from Dopa 1 or dopamine 3, are distinguished from the yellow to brown phaeomelanins obtained from Dopa in the presence of cysteine. Characteristic of eumelanins are the indole units, which are formed from catecholamines by intramolecular addition of the amino groups to the oxidatively generated o-quinones. [...]
Langmuir-Blodgett multilayers of hydrocarbon and fluorocarbon polymers with hydrophilic spacer, lipid-polyelectrolyte complexes and mesogenic polymers have been prepared. The thermal behaviour of the multilayers was studied by small angle X-ray scattering, IR and UV—visible spectroscopy. Good thermal stabilities were found for the various classes of polymers. In addition, for both complexed multilayers and mesogenic polymer films, reorientation processes were observed.
Contents: 1. Discotic Liquid Crystals 2. Monolayers and Langmuir-Blodgett Multilayers 3. Theoretical Considerations on the Molecular Packing of Discotic LCs in Monolayers and Multilayers 4. Spreading Experiments with Discotic LCs 5. LB-Multilayers of Discotic LCs 6. Polymeric Discotic LCs 7. Summary
The piezoelectric and pyroelectric properties of oriented films possessing dipole moments are increasingly being used in pressure, acoustic, thermal and optical devices. The performance of these devices in many applications may be enhanced by thin-film technology.The developing Langmuir-Blodgett thin-film deposition technique offers the opportunity to obtain highly oriented and uniform organic-based films in the 10–5000 nm thickness range. Special techniques must be used, however, to assemble these molecules in such a way as to result in polar multilayer films. Several possible deposition techniques are investigated, with one resulting in a polar and pyroelectric film about 50 nm thick.
Amphiphilic derivatives of octadiene and docosadiene were investigated in monolayers and Langmuir-Blodgett multilayers, with respect to their self-organization and their polymerization behavior. All amphiphiles investigated form monolayers. However, only acid and alcohol derivatives were able to build up multilayers. Those multilayers are rapidly photopolymerized in the layers via a two-step process: Irradiation with long-wavelength UV light yields soluble polymers, whereas additional irradiation with sfiort-wavelength UV light produces insoluble and presumably cross-linked polymers. The reaction meclianism is discussed according to the polymer characterization by UV spectroscopy, small-angle X-ray scattering, NMR spectroscopy, and gel permeation chromatography. All multilayers undergo structural changes during the polymerization; substantial changes result in defects in the polymerized layers as observed by scanning electron microscopy. In contrast to the acids and alcohols, the deposition of monolayers of the aldehyde derivatives did not yield well-ordered multilayers, but rather amorphous films. In this different film structure, the photopolymerization process differs from the one observed in multilayers.
Several polymerizable lipids were synthesized and polymerized to amphiphilic homopolymers and to copolymers with the help of hydrophilic comonomers. The self-organization of these polymeric lipids was investigated in monolayers and Langmuir-Blodgett multilayers. The self-organization of these polymers in model membranes is due to hydrophilic spacer groups in the amphiphilic side groups as well as to hydrophilic spacer groups in the polymer backbone. Thus, highly ordered monolayers and LB-multilayers are easily obtained.
The inhibitory effect of sinefungin on juvenile hormone biosynthesis and development in locusts
(1987)
The antibiotic fungal metabolite sinefungin is a potent inhibitor of S-adenosylmethionine-acceptor methyltransferases. Its effect on insect metabolism and especially on corpora allata farnesoic acid methyltransferase, which catalyzes the penultimate step of juvenile hormone biosynthesis, was investigated in Locusta migratoria. Injection of sinefungin results in a delay of imaginal molt and in suppression of ovary development. Isolated corpora allata are unable to synthesize juvenile hormone III in the presence of more than 1.0 mM sinefungin. In a cell-free system containing the S-adenosylmethionine-dependent farnesoic acid methyltransferase from corpora allata sinefungin is a competitive inhibitor of the synthesis of methylfarnesoate with Ki of 1 μM.
Cinnamic acid moieties were incorporated into amphiphilic compounds containing one and two alkyl chains. These lipid-like compounds with photoreactive units undergo self-organization to form monolayers at the gas-water interface and bilayer structures (vesicles) in aqueous solutions. The photoreaction of the cinnamic acid moiety induced by 254 nm UV light was investigated in the crystalline state, in monolayers, in vesicles and in solution in organic solvents. The single-chain amphiphiles undergo dimerization to yield photoproducts with twice the molecular weight of the corresponding monomers in organized systems. The photoreaction of amphiphiles containing two cinnamic acid groups occurs via two mechanisms: The intramolecular dimerization produces bicycles, with retention of the molecular weight of the corresponding monomer. The intermolecular reaction leads to oligomeric and polymeric photoproducts. In contrast to the single-chain amphiphiles, photodimerization processes of lipoids containing two cinnamic acid moieties also occur in solution in organic solvents.
Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface
(1986)
Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed.
Oriented supramolecular systems-polymeric monolayers and multilayers from prepolymerized amphiphiles
(1986)
Oriented polymeric membranes were originally prepared by polymerization or polycondensation of preoriented monomers. The introduction of hydrophilic spacer groups into the polymeric amphiphiles allowed the formation of highly ordered systems (monolayers, liposomes, multilayers) from prepolymerized amphiphiles: due to the partial decoupling of the different mobilities and orientation tendencies of the polymer chain and the amphiphilic side groups, these polymers are able to self-organize. In monolayer experiments the high order of these membranes could be demonstrated by their surface pressure area-diagrams. In addition the combination of order and mobility of these spacer groups containing polymeric amphiphiles allowed the formation of Langmuir-Blodgett-multilyers with a high layer correlation. Thus, disturbancies in highly oriented layers can be avoided normally taking place during the polymerization reaction (e.g. contractions) or oriented monomeric layers.
Langmuir-Blodgett multilayers of polymerizable carboxylic acids with hydrocarbon or fluorocarbon chains were prepared. The multilayers were polymerized by UV light and the reactions were studied by UV/visible spectroscopy. The polyreactions strongly influence the multilayer structures which were investigated by X-ray small-angle scattering and scanning electron microscopy. The spreading behaviour of the monomers, the preparation of multilayers, their reactivities in multilayers and structural effects caused by the polyreactions are discussed with regard to the hydrophilic head groups, the polymerizable groups and the hydrophobic chains.
A variety of polymerizable lipids containing a hydrophilic spacer group between the reactive group and the main amphiphilic structure have been synthesized. They were investigated in monolayers, liposomes, and multilayers. When the spacer concept was used, efficient decoupling of the motions of the polymeric chain and the amphiphilic side groups is achieved. Thus, the often found loss of the important fluid phases by polymerization is avoided. Polymeric monolayers of the spacer lipid, prepared either by polymerization in the monolayer or by spreading of prepolymerized lipid, exhibit nearly identical surface pressure-area diagrams. Most distinctly, the successful decoupling of the motions of the polymer main chain and the membrane forming amphiphilic side groups is demonstrated by the self-organization of bulk polymerized spacer lipids to polymeric liposomes. In addition, spacer lipids are able to build polymeric Langmuir-Blodgett multilayers. The decoupling of the polymer main chain and the membrane-forming amphiphilic side groups enables the deposition of already polymeric monolayers onto supports to form defined multilayers. If, alternatively, monomeric monolayers are deposited and polymerized on the support, defects in the layers due to structural changes during the polymerization are avoided by the flexible spacer group.
Sinefungin inhibited the S-adenosylmethionine-dependent farnesoic acid methyltransferase in a cell-free system containing a homogenate of corpora allata from female locusts, Locusta migratoria. The enzyme catalyzed the penultimate step of juvenile hormone biosynthesis in the insects. Culturing corpora allata in the presence of sinefungin greatly suppressed juvenile hormone production. The following in vivo effects were visible after injection of the inhibitor: increase in mortality and reduction of total haemolymph protein liter and ovary fresh weight, as well as length of terminal oocytes. Attempts to reverse these effects by topical application of the juvenile hormone analog ZR-515 (methoprene) were only partly successful. Therefore, the in vivo effects may be due to a general inhibition of methyltransferase enzymes in the insect. Sinefungin appeared to be of potential interest as the first representative of a new class of insect growth regulators.
The haemolymph of the adult Colorado potato beetle, Lepinotarsa decemlineata Say, contains a high molecular weight (MW > 200,000) JH-III specific binding protein. The Kd value of the protein for racemic JH-III is 1.3 ± 0.2 × 10−7 M. It has a lower affinity for racemic JH-I and it does not bind JH-III-diol or JH-III-acid. The binding protein does discriminate between the enantiomers of synthetic, racemic JH-III as was determined by stereochemical anaysis of the bound and the free JH-III. Incubation of racemic JH-III with crude haemolymph results in preferential formation of (10S)-JH-III-acid, the unnatural configuration. The JH-esterase present in L. decemlineata haemolymph is not enantioselective. It is concluded that the most important function of the binding protein is that of a specific carrier, protecting the natural hormone against degradation by esterases. The carrier does not protect JH-I as efficiently as the lower homologue.
[1-14C]-N-Acetyldopamine (NADA) was oxidized in the presence of methyl [3-3H]-β-alanate with mushroom tyrosinase. The complex mixture of reaction products was partly resolved by chromatographic procedures and analyzed by spectroscopic methods. Methyl-β-alanate is incorporated to only a small extent into oxidation products of NADA which inter alia are presumed to be oligomeric hydroxyquinones. After oxidation of [1-14C, 2-3H]-NADA with preparations from tanning Manduca sexta pupal cuticle, N-acetylnoradrenalin was identified as one of the products. Binding of radioactivity to melanin-like material was also observed. These results suggest that oxidation products different from those formulated usually for the crosslinkages between protein amino groups and N-acetyldopaquinone are deposited in darkly brown coloured insect cuticles during sclerotization.