Preparation of stimuli-responsive protein nanogel by quantum-ray irradiation

To prepare the functional nanoparticle with biological affinity, we tried to control the particle diameter and volume phase transition point of protein nanogel by quantum-ray irradiation. We succeeded in controlling the particle diameter of gelatin nanogel in the range of 20–70 nm by gamma-ray irradiation. It was also found that the prepared gelatin nanogel reversibly swelled and shrunk by pH and temperature change. Volume phase transition point and swelling ratio were found to change, depending on the absorbed dose and gelatin concentration.     

Temperature depending light scattering measurements of aqueous gelatin and alginate solutions and their mixtures

Highly diluted solutions of an alkaline treated pig bone gelatin and a seaweed alginate of Macrocystis pyrifera have been investigated by means of static light scattering at various temperatures. With these results the thermodynamic properties found by other authors and us before can be verified. Furthermore, diluted mixtures of both polymers with different ratios of composition have been investigated. These measurements show that both polymers in all mixtures behave quasi-binarily in the investigated temperature range. They maintain their association phenomena of the pure polymer solutions.     

Biodegradation of three-layer laminate films based on gelatin under indoor soil conditions

Three-layer gelatin films, composed of sodium montmorillonite (MMt) - plasticized gelatin (Ge-5MMt) (inner layer) and dialdehyde starch (DAS) - cross-linked and plasticized gelatin films (Ge-10DAS) (outer layers), obtained by heat-compression molding, were submitted to degradation under indoor soil burial conditions for 14 days. Biodegradation of multilayer film as well as individual components and control gelatin films was evaluated by monitoring water absorption and weight loss. It was established that technological treatments performed on gelatin, such as cross-linking, compounding with clay and heat-compression molding have a major impact on the biodegradation rate and extent. The possible reasons are discussed. Weight loss results revealed that the susceptibility to microbial attack during soil burial varied in the order: Ge-10DAS < multilayer < Ge-5MMt < gelatin control film. The intermediate behaviour of the multilayer was associated with the presence of hydrogen-bonding interactions between layers, induced by processing. Scanning electron microscopy revealed that the multilayer was preferentially biodegraded by filamentous microorganisms and even larvae in the later stages of the process. The presence of holes and pits on the multilayer surface was more likely attributed to the preferential removal of glycerol and DAS as shown by thermogravimetric analysis.     

Dynamic behavior of surface charge on gamma-ray irradiated polybutylene naphthalate

Polymer insulating materials used in radioactive environment can be degraded by discharge which is induced by surface charge accumulation. Hence the stability of the electrical insulation is dependent upon the dynamic behavior of surface charge that may be changed by irradiation. In this paper, polybutylene naphthalate was employed as test sample to investigate the effects of gamma-ray irradiation on the charge behavior. The samples were previously irradiated in air up to 100 kGy and then up to 1000 kGy with dose rate of 10 kGy/h using a ⁶⁰Co gamma-source. The experiment was carried out under a negative dc stress between two aluminum plate electrodes. An electrostatic probe was designed to measure the charge density. Obtained results show that with the increase of the total dose of the irradiation, both the capacity of surface charge and the rate of charge decay decrease. It is proposed that the charging behavior depends upon the density of localized surface states that is reduced by the radiation induced cross-linking reactions. The decay is caused by the recombination of surface charge with ions of the opposite sign in air.     

Surfactant induced softening in gelatin hydrogels

Effect of binding of three surfactants, alpha olefin sulfonate (AOS, anionic), Triton-X100 (TX-100, non-ionic) and cetyl trimethyl ammonium bromide (CTAB, cationic) to the hydrogels of gelatin was studied at room temperature (25 °C) by dynamic light scattering and oscillatory rheology with surfactant concentrations (20-100 mM) much larger than the critical micellar concentrations (cmc) of these surfactants. The measured intensity auto-correlation function of light scattered from gels revealed the presence of finite heterodyne contribution ≈0.11 ± 0.01 that increased to ≈0.25 ± 0.02 after transition to the soft gel state indicating a softening process for surfactant concentrations exceeding 50 mM. The dynamic structure factor S(q, t) of micelle bound gelatin gels revealed two clearly identifiable relaxation modes namely; the fast mode, S(q, t) ∼ exp · (−D_fq²t) for t ? 1 ms and a stretched exponential mode, S(q, t) ∼ exp · −(t/τ_c)^β for 1 ms ? t ? 1 s. This behaviour was universal with β ≈ 0.85 ± 0.04 independent of the surfactant type. The low frequency (1.5 rad/s) storage modulus G′, loss modulus G″ and tan δ behaviour revealed a gradual softening of the gel independent of the surfactant type. The exponent (β) fast mode diffusivity (D_f) and stretched exponential mode relaxation time were found to be less sensitive to this softening transition.     

Comparison of γ-radiation and electron beam irradiation effects on gelatin

Gelatin is a heterogeneous mixture of water-soluble proteins of high average molecular weight derived by hydrolytic action from collagen, a protein of mammal external protective tissues. There are many characteristics of a material that can indicate its quality or performance in its intended use. The knowledge of a material's rheological characteristics is valuable to predict its pourability, its performance in a dipping or coating operation or the ease with which it may be handled, processed or used. In this work bovine powder gelatin was submitted to γ-radiation from a ⁶⁰Co source, dose rate about 7 kGy/h and to electron beam irradiation, dose rate about 11 kGy/s. The doses applied were 5, 10, 20 and 50 kGy. The radiation effects were measured following viscosity changes at 40°C of gelatin powder 10% aqueous solutions. The relationship between the decrease in viscosity of gelatin solutions and radiation dose presented close comparable values for both irradiation processes.     

Preparation of gelatin/poly(vinyl alcohol) film modified by methyl methacrylate and gamma irradiation

The properties of gelatin–polyvinyl alcohol (G–PVA) blend films were improved by methyl methacrylate (MMA) and γ irradiation for a practical viewpoint. The films were prepared by the casting method, modified by glycerol and MMA monomer, and their mechanical properties were also studied. The gelatin-based films were successfully prepared using γ irradiation (3.1 kGy) and gelatin: PVA = 97:3 (w/w) as optimized. Tensile properties of the films were studied and thermal properties of the films were characterized by thermogravimetric analysis and dynamic mechanical analysis pointed out that MMA treated both gelatin films, and G–PVA blend films showed less thermal degradation than untreated films. In addition, structural and morphological features of the gelatin-based films were examined by Fourier transform infrared and scanning electron microscopy, respectively. The ultimate results of the present study showed remarkable enhancement in tensile properties (> 40%) and a reduction in elongation at break of the films, thanks to the MMA addition and γ irradiation.     

The size and shape of silica particles

Negatively charged silica particles were investigated at pH 10.0. They were found to be rod-shaped (cylinder) with a diameter of 5–5.5 nm and a full length of 44–67 nm depending on the rod model used. Moreover, the particles were found to be stable against aggregation in the region 0.4–50 mM NaCl. Received: 2 December 1998 Accepted in revised form: 2 February 1999     

Quasielastic light scattering study of chemically crosslinked gelatin solutions and gels

Quasielastic light scattering measurements are reported for experiments performed on mixtures of gelatin and glutaraldehyde (GA) in the aqueous phase, where the gelatin concentration was fixed at 5 (w/v) and the GA concentration was varied from 1×10⁻⁵ to 1×10⁻³ (w/v). The dynamic structure factor, S(q,t), was deduced from the measured intensity autocorrelation function, g ₂(τ), with appropriate allowance for heterodyning detection in the gel phase. The S(q,t) data could be fitted to S(q,t)=Aexp(−D _f q ² t)+Bexp(−t/τ_c)^β, both in the sol (50 and 60 ^∘C) and gel states (25 and 40 ^∘C). The fast-mode diffusion coefficient, D _f showed almost negligible dependence on the concentration of the crosslinker GA; however, the resultant mesh size, ξ, of the crosslinked network exhibited strong temperature dependence, ξ∼(0.5−χ)^1/5exp(−A/RT) implying shrinkage of the network as the gel phase was approached. The slow-mode relaxation was characterized by the stretched exponential factor exp(−t/τ_c)^β. β was found to be independent of GA concentration but strongly dependent on the temperature as β=β₀+β₁ T+β₂ T ². The slow-mode relaxation time, τ_c, exhibited a maximum GA concentration dependence in the gel phase and at a given temperature we found τ_c(c)=τ₀+τ₁ c+τ₂ c ². Our results agree with the predictions of the Zimm model in the gel case but differ significantly for the sol state. Received: 25 May 1999 /Accepted in revised form: 27 July 1999     

Properties of complexes and particles of gelatin with ionic surfactants

 The properties of soluble gelatinionic surfactant complexes and insoluble particles were evaluated. It was found that colloidal particles of gelatin A – cationic surfactant (dodecyltrimethyl-ammonium bromide, DTAB, and cetyltrimethylammonium bromide, CTAB) were formed. Binding isotherms showed that these particles are obtained above the CMC of each surfactant, while cooperative binding takes place. Surface tension measurements conducted for both gelatin/DTAB and gelatin/anionic surfactant, SDS (sodium dodecyl sulfate) showed a break in the curve describing surface tension vs number of bound surfactant molecules, (ν) at concentrations below the CMC of each surfactant alone. This break, which is attributed to CMC 1, is observed at the same number of bound surfactant mol ecules ν∼2 for both gelatin/surfactant couples. Contact angle measurements showed that the maximal hydro-phobicity of the gelatin-surfactant particles is obtained at the same concentration range in which the precipitation occurs. It was also found that the hydrophobicity of gelatin-SDS particles, is higher than that of the gelatin-cationic surfactants, due to a different composition of the resulting particles. The zeta potential of the particles indicated charge neutralization and even charge reversal for gelatin-CTAB at high surfactant concentration. Received: 4 April 1997 Accepted: 15 December 1997     

UV irradiation enhances the bonding strength between citric acid-crosslinked gelatin and stainless steel

The effect of ultraviolet ray (UV) irradiation on the bonding strength between low carbon stainless steel 316 (SUS316L) and trisuccinimidyl citrate (TSC)-crosslinked alkali-treated gelatin (AlGelatin-TSC) was investigated. The UV irradiation effectively generated hydroxyl groups on the surface of SUS316L. The bonding strength between AlGelatin-TSC and SUS316L before UV irradiation was 0.345±0.007 MPa, and upon UV irradiation it increased to 0.750±0.069 MPa. In order to explain this enhanced bonding strength, the surface of SUS316L was examined using its water contact angle and X-ray photoelectron spectroscopy. Furthermore, the N 1s peaks derived from the TSC succinimidyl group were assigned to the surface of SUS316L after the immobilization of the TSC. This indicates that ester bond formation between the TSC active esters and the SUS316L hydroxyl groups contributed to the enhanced bonding strength. Therefore, UV irradiation and subsequent TSC immobilization is a simple way to functionalize biometal surfaces with various structures. This has practical applications for medical devices such as drug-eluting stents, dental implants, and metallic artificial bone.     

Monodisperse thermosensitive particles prepared by emulsifier-free emulsion polymerization with microwave irradiation

The emulsifier-free emulsion polymerization of styrene (St) and N-isopropylacrylamide (NIPAAm) was successfully carried out with microwave irradiation, and the monodisperse thermoresponsive poly(styrene-co-N-isopropylacrylamide) (poly(St-co-NIPAAm)) particles with diameters in the range 100–130 nm were prepared. The morphology, size and size distribution of the poly(St-co-NIPAAm) particles were characterized by transmission electron microscopy, scanning electron microscopy (SEM) and photon correlation spectroscopy (PCS), respectively. The results showed that poly(St-co-NIPAAm) particles had spherical morphology, and the poly(St-co-NIPAAm) particles prepared by emulsifier-free emulsion polymerization with microwave irradiation were smaller, more uniform than those obtained with conventional heating. The hydrodynamic diameters of poly(St-co-NIPAAm) particles were decreased as the temperature increased from 25 °C to 40 °C, and poly(St-co-NIPAAm) particles collapsed remarkably at 32 °C, which is the lower critical solution temperature of the poly(N-isopropylacrylamide). The morphology of the assembled poly(St-co–NIPAAm) particles was observed by SEM, it was found that monodisperse poly(St-co-NIPAAm) particles could assemble to form the two-dimensional order structures.     

静电纺羟基磷灰石/明胶微纳复合纤维

本文从仿生角度出发,模拟细胞外基质独特结构,采用静电纺丝法成功制备出HA均匀分布的HA/Gelatin复合纤维。根据影响静电纺丝的主要因素,分别考察了聚合物浓度、无机物含量、溶剂浓度、电纺电压等因素对纤维形貌和结构的影响。研究结果表明:聚合物浓度是制备复合纤维的首要影响因素,影响复合纤维的直径;无机物的添加使聚合物中的氢键减少,降低了电纺液的粘度,影响复合纤维中珠状物的形成;制备分布均匀的电纺纤维,溶剂起很大的作用,影响纤维的粘联;电纺电压增大使电场力过大,聚合物被强力拉伸,单根纤维出现卷曲。     

Colloidal crystals made of poly(N-isopropylacrylamide) microgel particles

Poly (N-isopropylacrylamide) microgel particles are found to form colloidal crystals similar to those occurring in typical hard-sphere colloids like poly(methylmethacrylate) beads. Samples made of particles with different cross-linker concentrations are investigated and their deswelling ratio is determined using dynamic light scattering. Small-angle neutron scattering data are also presented and analysed in terms of a face-centred-cubic crystal structure. The characteristic length, a, of the elementary cell is found to be 535 ± 16 and 495 ± 15 nm for the two systems investigated. This leads to particle radii of 189 ± 6 and 175 ± 5 nm, respectively. These values compare well to the radii determined using several different methods. Received: 26 July 1999/Accepted: 21 March 2000     

湿法消解测定食用明胶中的微量铬

建立了一种以HNO3-H2SO4-HClO4体系湿法消解食用明胶, 并采用分光光度计测定其中微量铬的新方法. 该方法的相对标准偏差1.8%～5.9%, 回收率93.3%～104.7% (n=8), 同时与原子吸收光谱法对照实验的误差均在4%以下. 本法可测定食用明胶中的微量铬.     

Evidence for hydrophobic attraction between latex particles in aqueous systems as investigated by turbidimetry

We report the evidence for attractive interaction of latex particles which are covered by poly(ethylene oxide) chains. These particles are suspended in aqueous solutions of ammonium sulfate. The interaction is probed by measurements of the turbidity of the suspensions up to 70 g/l. Turbidity is insensitive to multiple scattering and allows the static structure factor, S(q) [q=(4πn ₀/λ₀)sin(θ/2), where θ is the scattering angle, n₀ is the refractive index of the medium and λ₀ is the wavelength in vacuo], to be determined at small q values. The analysis of S(q) at small q values yields information about possible attraction of the particles. The analysis of the turbidity data furthermore shows that no aggregation took place in these systems. A weak but long-range attractive interaction was found at ammonium sulfate concentrations of 0.01 and 0.1 M. The relation of this attractive force to hydrophobic forces is discussed. Received: 9 March 2000/Accepted: 28 June 2000     

Effects of aromatic diacetylenes on polyurethane degradation by gamma irradiation

The effects of four aromatic diacetylenes on the gamma-irradiation-induced degradation of a commercial polyurethane were studied. Addition of 1 wt% of diphenylbutadiyne, which is homogeneously distributed in the polymer, effectively suppressed the polymer chain degradation. The dose required to decrease tensile strength by 50% was found to be 582 kGy for the polyurethane with 1 wt% of diphenylbutadiyne, while a dose of only 310 kGy for the polyurethane itself. The Young's modulus of the polyurethane alone decreased with dose; meanwhile the films with diphenylbutadiyne did not change. The films with p,p′-dinitrodiphenylbutadiyne behaved differently from others due to their inhomogeneous composition. The amide substituted diacetylenes also showed protecting effect, but in less extent due to the steric effect.     

Study on facile designing,swelling properties and structural relationship of gelatin nanoparticles

In the present work glutaraldehyde crosslinked gelatin (Type-A and Type-B) nanoparticles were fabricated following a microemulsion crosslinking technique. The structural, morphological, and stability features of nanoparticles were investigated using the techniques like FTIR, TEM, XRD, DLS, and surface charge measurements. The spectral peaks appeared in the FTIR spectra of gelatin nanoparticles confirmed the crosslinking of gelatin molecules with glutaraldehyde. The SEM analysis of the nanoparticles suggested that the size of gelatin nanoparticles was nearly 300 nm whereas the TEM analysis revealed their size around 200?nm. The size of nanoparticles was found to increase with increasing amounts of gelatin while it showed a decrease when the concentration of crosslinker was increased. An increase in percent crystallinity was observed when gelatin was crosslinked with glutaraldehyde. The water uptake capacity of the gelatin nanoparticles was evaluated under varying experimental conditions like, pH, temperature, presence of simulated physiological fluids and varying composition of the gelatin nanoparticles. To study the cytotoxic behavior of gelatin nanoparticles in vitro cytotoxicity analysis were performed. The gelatin nanoparticles demonstrated good stability and biocompatibility which suggested that these particles can be used as drug carrier in fabricating a swelling controlled drug delivery system.     

Study of the degradation of gelatin in paper upon aging using aqueous size-exclusion chromatography

We studied the aging behaviour of gelatin used to size paper. Thus far, research on the aging of paper has largely ignored the sizing agent. Degradation of the protein was characterised and the impact of paper components, such as cellulose, and aluminium potassium sulphate was evaluated. Whatman No. 1 filter papers sized with two types of gelatins (A and B) were prepared as model samples. Commercially sized modern papers (Arches) were also studied in order to compare laboratory samples with real artist papers. Both types of papers were artificially aged (80 °C, 50% relative humidity for 35 and 94 days). Historic papers were included in the study in order to compare artificially aged with naturally aged gelatin. The aqueous extracts from the papers were characterised by aqueous size-exclusion chromatography (SEC) using four PL-Aquagel-OH columns and UV photodiode array detection at 220, 254 and 280 nm. Results showed that gelatin undergoes hydrolysis upon aging, type A gelatin showing a faster degradation rate than type B. The result was an increase in the lower-molar-mass fractions, under 50 000 g mol⁻¹, and especially in a characteristic fraction with a peak molecular mass (M_p) of 14 000 g mol⁻¹. A significant decrease in the extraction yields of -, β- and γ-chains occurred after aging. This was attributed to crosslinking, leading to the formation of less-soluble polypeptides with very high molar mass (>800 000 g mol⁻¹). Less than 10% alum had no impact on the degradation rate; higher alum contents accelerated hydrolysis reactions.