Shorter Gelation Time Research Articles

Performance optimization of injectable chitosan hydrogel by combining physical and chemical triple crosslinking structure

To improve the biocompatibility and application properties of injectable chitosan hydrogel, an injectable triple crosslinking network hydrogel (CTGP) is prepared by physical interaction, Michael addition and disulfide bond formation based on thiolated chitosan (CS-TGA), β-glycerophosphate (β-GP) and poly(ethylene glycol) diacrylate (PEGDA) without the addition of cytotoxic crosslinkers and catalysts. Compared with the short gelation time of 2 min of CTG hydrogel (without PEGDA) at 37°C, CTGP hydrogel containing different molecular weight of PEGDA exhibits controllable gelation times from 1 to 22 min, which could meet the different demands in clinical application. Further, the compressive modulus is improved differently by introducing PEGDA into the system. The presence of PEGDA in CTGP hydrogel imparts better swelling property, and there is a sustained protein release from the hydrogel without any initial burst. In vitro cytotoxicity and hemolysis reveal that the gel is biocompatible. In vivo subdermal injection into mice models further confirms the non-cytotoxicity of the hydrogel and the hydrogel is highly resistant to degradation.

A Crown Ether Appended Super Gelator with Multiple Stimulus Responsiveness

A crown ether appended super gelator is designed and synthesized. It can gel a variety of organic solvents and shows excellent gelation properties with both low critical gelation concentration and short gelation time. Due to the introduction of the crown ether moiety and a secondary ammonium unit, the supramolecular gels show reversible gel-sol transitions. The supramolecular gels can also be molded into shape-persistent and free-standing objects.

Gelation behaviour and rheological properties of acid-induced soy protein-stabilized emulsion gels

The protein concentration dependence on the rheological properties of acid-induced gels formed with unheated and heated soy protein-stabilized emulsions (UHSPE and HSPE) was investigated at different acidification temperatures. Pre-heat treatment on soy protein solutions resulted in a higher storage modulus (G′) and a shorter gelation time (tgel) of acid-induced emulsion gels. A maximum in tan δ was observed in the UHSPE gels but no maximum was detected in the HSPE gels. Increasing the acidification temperature decreased the G′ and tgel. The dependence of the G′ on the protein concentration (c) can be scaled with a power law: G′ ∼ cA. The exponent (A) increased with pre-heat treatment and acidification temperature. The experimental data.fitted the fractal scaling model (G′ ∼ φA) and the simple time- scaling model above very well for the acid-induced soy protein-stabilized HSPE gels with varying oil volume fraction. The large deformation and fracture properties were significantly affected by soy protein concentration, pre-heat treatment, acidification temperature and volume fraction of oil droplets (p < 0.05).

Sodium dodecyl sulfate-induced rapid gelation of silk fibroin

The in situ formation of injectable silk fibroin (SF) hydrogels have potential advantages over various other biomaterials due to the minimal invasiveness during application. Biomaterials need to gel rapidly under physiological conditions after injection. In the current paper, a novel way to accelerate SF gelation using an anionic surfactant, sodium dodecyl sulfate (SDS), as a gelling agent is reported. The mechanism of SDS-induced rapid gelation was determined. At low surfactant concentrations, hydrophobic interactions among the SF chains played a dominant role in the association, leading to decreased gelation time. At higher concentrations of surfactant, electrostatic repulsive forces among micellar aggregates gradually became dominant and gelation was hindered. Gel formation involves the connection of clusters formed by the accumulation of nanoparticles. This process is accompanied by the rapid formation of β-sheet structures due to hydrophobic and electrostatic interactions. It is expected that the silk hydrogel with short gelation time will be used as an injectable hydrogel in drug delivery or cartilage tissue engineering.

Properties of phenol‐formaldehyde resins prepared from phenol‐liquefied lignin

AbstractIn this study, alkaline lignin (AL), dealkaline lignin (DAL), and lignin sulfonate (SL) were liquefied in phenol with sulfuric acid (H2SO4) or hydrochloric acid (HCl) as the catalyst. The phenol‐liquefied lignins were used as raw materials to prepare resol‐type phenol‐formaldehyde resins (PF) by reacting with formalin under alkaline conditions. The results show that phenol‐liquefied lignin‐based PF resins had shorter gel time at 135°C and had lower exothermic peak temperature during DSC heat‐scanning than that of normal PF resin. The thermo‐degradation of cured phenol‐liquefied lignin‐based PF resins was divided into four temperature regions, similar to the normal PF resin. When phenol‐liquefied lignin‐based PF resins were used for manufacturing plywood, most of them had the dry, warm water soaked, and repetitive boiling water soaked bonding strength fitting in the request of CNS 1349 standard for Type 1 plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Experimental and Numerical Investigations of Ground Deformation Using Chemical Grouting for Pipeline Foundation

Based on experimental and numerical investigations, the present paper focuses on under ground scope (UGS) chemical grouting method that can actually improve the pipeline surrounding foundation to solve pipeline saggy damage. According to the experimental results, a solution-type injection material could make lager soil deformation, using less total slurry amount than suspension-type injection material. Therefore, a suspension-type injection material with shorter gel time is more suitable for the UGS method, making it more effective to reinforce the pipeline foundation and restore pipelines. The results of some patterns of injection tests revealed relationship between the behavior of the grouting material and the deformation of the soil. It is found that the material can be injected into a foundation by fracture grouting if the permeation coefficient is lower than 1.00 × 10−3 mm/s. The situation was analyzed by using 2-D finite element method analysis software Phase2, and the analysis result proposes that the real data and simulation data are nearly the same in impermeable soil. Furthermore, even if the construction object is permeable soil, it can also be become impermeable soil by two phases grouting: soil improvement grouting and restoration grouting.

Photopolymerization of Bis(4-methacryloylmethylphenyl)sulfide and Bis(4-methacryloylmethylphenyl)sulfone with Vinyl Monomers and Properties of the Prepared Copolymers

The reaction of photopolymerization of bis(4-methacryloylmethylphenyl)sulfide (BMcMPhS) and bis(4-methacryloylmethylphenyl)sulfone (BMcMPhSu) with the typical vinyl monomers: methyl methacrylate (MMA) and styrene (St) in the presence of the two photoinitiators: Irgacure 651 and Darocur 1173 are presented. The influence of percentage concentration of BMcMPhS and BMcMPhSu on the gelation times of the prepared copolymers was studied. The effect of the used photoinitiator concentrations on gelation times was also investigated. For the chosen copolymers, mechanical properties including tensile strength, elongation at break, Young modulus, Brinell's and Shore's hardness were determined. The results showed that copolymers with MMA had shorter gelation times than those with St. Gelation times were shorter when Darocur 1173 was used as a photoinitiator. An increase of Darocur 1173 concentration caused a decrease of gelation times, whereas in the case of Irgacure 651 the opposite relation was observed.

Rheological properties and permeability of soy protein-stabilised emulsion gels made by acidification with glucono-δ-lactone

Soy protein, an important efficient emulsifier, is widely used by the food industry for incorporation into milk, yogurts, ice cream, salad dressings, dessert products, etc. The objective of this study was to investigate the rheological and physical properties of soy protein-stabilised emulsion gels as affected by protein concentration and gelation temperature. The rheological properties and permeability were determined using oscillatory rheometry, permeability and whey separation. The modulus (G' and G″), fracture stress and fracture strain of acid-induced emulsion gels after 20 h of glucono-δ-lactone addition depended strongly on soy protein concentration and gelation temperature. At increasing soy protein concentrations, acid-induced emulsion gels had shorter gelation times but higher storage moduli (G'), fracture stresses and strains. Increasing gelation temperature decreased the gelation time, G', fracture stresses and strains. Permeability and whey separation were significantly affected by the protein concentration and the gelation temperature. A significant positive correlation was observed between whey separation and permeability coefficient in emulsion gels formed at different temperatures. The rheological properties and permeability of soy protein-stabilised emulsion gels were significantly influenced by protein concentration and gelation temperature.

Characterization of phenol–formaldehyde resins derived from liquefied lodgepole pine barks

In this study, lodgepole pine ( Pinus contorta Dougl.) barks with and without infestation by mountain pine beetle (MPB, Dendroctonus ponderosae Hopkins) were liquefied in phenol with sulfuric acid. The liquefied portions of the bark were used to synthesize bark-derived phenol–formaldehyde (BPF) adhesive resins under alkaline conditions. In comparison to a commercial phenol–formaldehyde (PF) resin and a lab PF resin, the BPF resins were found to have larger average molecular weights, higher polydispersity indices and shorter gel times. The viscosities of the BPF resins were higher than the viscosity of the lab PF resin but lower than the viscosity of the commercial PF resin. Isothermal DSC tests indicated that all resins exhibited both nth-order and autocatalytic cure mechanisms. The post-curing thermal stability of the BPF resins was similar to that of the lab PF resin at higher temperatures but differed significantly from that of the commercial PF resin. All these resins had similar dry bonding strengths; the BPF resins showed the highest wet bonding strengths. Beetle infestation was shown to have no negative effect on the bonding properties of the BPF resins.

Monitoring and Modeling Grout Efficiency of Lifting Structure in Soft Clay

An inclined eight-story reinforced concrete building on a thick soft clay deposit was leveled by compensation grouting with short gel time grout injected through sleeved pipes. The monitoring system is used to record the injected grout volume, the mat foundation’s heaved volume after grouting, and the mat foundation’s settled volume during pore pressure dissipation. The grouting efficiencies improved from negative value to less than one, and the stress histories of clay soils changed from normally consolidated to overconsolidated states. A final compensation efficiency of 9.78% was achieved and the building was successfully leveled. A series of numerical simulations were conducted to assess the capability of compensation grouting modeling. The numerical simulation results indicate that the consolidation behavior and the stress history of clayey foundation soils can be modeled reasonably well. However, the computed final grout efficiency is larger than that from the monitoring data because the simulation of fracture grouting by volumetric strain input is more like compaction grouting mode rather than fracture grouting mode, and this induces lesser excess pore pressure, lesser settlement and higher grout efficiency. These findings are also confirmed from other researchers’ laboratory and field testing results.

Fast Curing Phenol-Formaldehyde Resin Catalyzed by a Complex Catalyst

For increasing the curing rate and decreasing the curing temperature, modified phenol-formaldehyde (PF) resins were synthesized under a complex catalyst. The bonding strength and formaldehyde emission of the plywood bonded by them were measured according to Chinese National Standards methods. The curing behavior was conducted by differential scanning calorimetry (DSC) measurement. The results indicate that PF resins catalyzed by the complex catalyst show more moderate pH values, lower curing temperature and shorter gel time comparing with control ones. Plywood bonded with modified PF resins shows good bonding strength and low formaldehyde emission even at low hot press temperature (110 °C), which is closed to the plywood bonded with normal control PF resin at high hot press temperature (130 °C).

The effects of solvents on the formation of sol–gel-derived Bi 12SiO 20 thin films

The sol–gel method was used to synthesize Bi 12SiO 20 thin films. Two synthesis routes with two different solvents, i.e., 2-ethoxyethanol and acetic acid, were used and compared. Thin films were deposited onto Pt/TiO 2/SiO 2/Si substrates by spin-coating at 3000 rpm and annealed at 700 °C for 1 h. A different coordination of the bismuth ion was observed in the sols prepared with acetic acid (AcOH), and as a result, stable sols were formed with a shorter gelation time t G = 84 h ( c = 0.76 M), when compared with the sols prepared from 2-ethoxyethanol (EtoEtOH) t G = 580 h ( c = 0.76 M). The microstructures of the Bi 12SiO 20 thin films prepared from sols using EtoEtOH were homogeneous and dense. On the other hand, a porous microstructure was observed for the Bi 12SiO 20 thin films deposited from the sol in which AcOH was used as the solvent.

Gelation behavior with acetylation of chitosan for membrane preparation

The aim of this work is to investigate the gelation behavior of chitosans which has various degree of acetylation (DA) of amino group to ensure the preparation of the designed membrane structure. The DA was controlled by the amount of acetic anhydride added to the solution of chitosan/acidified water/methanol mixture. The gelation behavior was evaluated by the gelation time and the quantity of syneresis. The mechanical strength of acetylated chitosan gels was also measured. The optimum condition for the formation of the membrane, i.e. chitosan concentration, acetic acid/ chitosan mass ratio, methanol/water mass ratio, and amount of acetic anhydride for acetylation, was determined. This composition gives low contractility, shorter gelation time, and high mechanical strength to the membrane and the gel. Useful information not only for a preparation of a membrane but also for an immobilized carrier or a chemical reaction system was obtained in this work.

Castor oil-based thermosets with varied crosslink densities prepared by ring-opening metathesis polymerization (ROMP)

Two castor oil-based monomers, (1) norbornenyl-functionalized castor oil (NCO), which has ∼0.8 norbornene rings per fatty acid chain and (2) norbornenyl-functionalized castor oil alcohol (NCA), which has ∼1.8 norbornene rings per fatty acid chain, have been prepared. Ring-opening metathesis polymerization (ROMP) of different ratios of NCO/NCA using the 2nd generation Grubbs catalyst results in rubbery to rigid biorenewable-based plastics with crosslink densities ranging from 318 to 6028mol/m3. Increased crosslink densities result in shorter gelation times, better incorporation of the monomers into the polymer network, and much less soluble materials in the bulk materials. The increased crosslink densities obtained by adding NCA enhance the thermal properties, including the glass transition temperature (Tg) and room temperature storage modulus, which increase from −17.1°C to 65.4°C and from 2.4MPa to 831.9MPa, respectively. The TGA results, where T10 increased from 285°C to 385°C, illustrate that improved thermal stabilities can be obtained for thermosets with higher crosslink densities. Young’s modulus (11–407MPa), tensile strength (1.6–18MPa) and toughness (0.14–1.6MPa) are also improved dramatically with higher crosslink densities.

A study on the curing and viscoelastic characteristics of melamine–urea–formaldehyde resin in the presence of aluminium silicate nanoclays

Low viscosity melamine–urea–formaldehyde (MUF) resin for wood impregnation was synthesized and mixed with layered silicate nanoclays. Ball-milling of the nanoclays was performed to have a better dispersion of the nanoclays into the MUF resin. The effect of nanofillers both milled and unmilled, on the curing and viscoelastic properties of the MUF was investigated, using differential scanning calorimetry and dynamical mechanical thermal analysis methods. Two exotherms were observed during the MUF curing process. The apparent activation energy was lowered for the first exotherm at lower temperature, while increased for the second exotherm, with the addition of nanoclays into the MUF. Ball-milling of nanofillers resulted in an increased apparent activation energy and longer gel time for the milled organophilic nanoclay/MUF, but shorter gel time and better dynamic mechanical properties of the milled hydrophilic nanofiller/MUF, as compared to the correspondingly unmilled nanofiller/MUF systems. The storage modulus of all the nanofiller/MUF resins was considerably increased as compared to the neat MUF resin. This improvement is, however, more obvious for the surface modified layered silicate/MUF system, due to more compatible functional-groups grafted onto the nanoclays, and stronger layered silicate/MUF matrix adhesion, thus better performances were observed for the resulting nanoclay/MUF composites.

Kinetics of Sol-Gel Transformation for the Preparation of TiO&lt;sub&gt;2&lt;/sub&gt; Ultrafiltration Membrane

The sol-gel technique is considered to be one of the most practical methods for producing ceramic membranes, and the properties of the sols could affect the microstructures of the desired products. Especially, optimized viscosity and a short gelation time can reduce the sol particles infiltrate into the pores of the support. So how to control the forming process of the gel is essential for fabricating the membranes. In this paper, we developed a kinetic equation of sol-gel transformation to study the relationships between viscosity and time of titanium sol systems by using N, N—Dimethylformamide (DMF) as solvent. Both the growth process of the sol particles and activation energy of the process were investigated according to the kinetic curves. The results indicate that the viscosity of sols decreases with the increment of R and temperature, but increases with rw, at the same time the gelation time decreases with rw, temperature and R. Furthermore, the growth of sol particles versus time accord with the NLG model, and the activation energy of gelation process decreased with R. When R changed from 2 to 6, the activation energy was decrease from 12.48KJ/mol to 9.35KJ/mol. According to the analysis of the results of the sol-gel transformation, a shorter gelation time could be obtained by increaseing the rw, R and the gelation’ temperature.

Differential physical, rheological, and biological properties of rapid in situ gelable hydrogels composed of oxidized alginate and gelatin derived from marine or porcine sources

Marine derived gelatin is not known to associate with any communicable diseases to mammals and could be a reasonable substitute for gelatin derived from either bovine or porcine sources. The low melting point of marine gelatin (8 degrees C) also offers greater formulation flexibility than mammalian derived gelatins. However, the sub-optimal physical properties of marine gelatin generally limit the interest to further develop it for biomedical applications. This study aimed at investigating the feasibility of using oxidized alginate (Oalg) as a high activity macromolecular crosslinker of marine gelatin to formulate in situ gelable hydrogels with the goal of enhancing the latter's physical properties. The performance of Oalg/marine gelatin hydrogel was compared to Oalg/porcine gelatin hydrogel; in general, the physicomechanical properties of both hydrogels were comparable, with the hydrogels containing porcine gelatin exhibiting moderately higher mechanical strengths with shorter gelation times, smaller size pores, and higher swelling ratios. On the contrary, the biological performances of the two hydrogels were significantly difference. Cells cultured in the marine gelatin derived hydrogel grew significantly faster, with greater than 60% more cells by 7 days and they exhibited more spread-out conformations as compared those cultured in the porcine derived hydrogel. Production of ECM by cells cultured in the Oalg/marine gelatin hydrogel was up to 2.4 times greater than that of in the Oalg/porcine gelatin hydrogel. The biodegradation rate of the hydrogel formulated from marine gelatin was greater than its counterpart prepared from porcine gelatin. These differences have important implications in the biomedical applications of the two hydrogels.

Injectable chitosan-based hydrogels for cartilage tissue engineering

Water-soluble chitosan derivatives, chitosan- graft-glycolic acid (GA) and phloretic acid (PA) (CH-GA/PA), were designed to obtain biodegradable injectable chitosan hydrogels through enzymatic crosslinking with horseradish peroxidase (HRP) and H 2O 2. CH-GA/PA polymers were synthesized by first conjugating glycolic acid (GA) to native chitosan to render the polymer soluble at pH 7.4, and subsequent modification with phloretic acid (PA). The CH-GA43/PA10 with a degree of substitution (DS, defined as the number of substituted NH 2 groups per 100 glucopyranose rings of chitosan) of GA of 43 and DS of PA of 10 showed a good solubility at pH values up to 10. Short gelation times (e.g. 10 s at a polymer concentration of 3 wt%), as recorded by the vial tilting method, were observed for the CH-GA43/PA10 hydrogels using HRP and H 2O 2. It was shown that these hydrogels can be readily degraded by lysozyme. In vitro culturing of chondrocytes in CH-GA43/PA10 hydrogels revealed that after 2 weeks the cells were viable and retained their round shape. These features indicate that CH-GA/PA hydrogels are promising as an artificial extracellular matrix for cartilage tissue engineering.

Preparation of Mesoporous Carbon by Phenol Resin Polymerization-dependent Phase Separation and Pyrolysis

Porous carbon was prepared by technique of phenol resin polymerization-dependent phase separation and pyrolysis.The influence of catalyst amount on pore structure of porous carbon was investigated.The results show that porous carbons with average pore size of ca.40nm are obtained. The apparent porosity increases with increasing amount of catalyst.When the catalyst amount is 15%, apparent porosity of the porous carbon reaches 54.3%.Moreover,the carbon skeletons of the porous carbons become finer with high amount of catalyst.Volume shrinkage and gel time play important roles in changing the pore structure of porous carbons,for the porous carbons with high amount of catalyst have less shrinkage and shorter gel time during the curing.

Synthesis and characterization of matrix metalloprotease sensitive-low molecular weight hyaluronic acid based hydrogels

Hyaluronic acid is a naturally derived glycosaminoglycan (GAG) involved in biological processes. A low molecular weight hyaluronic acid (50 kDa)-based hydrogel was synthesized using acrylated hyaluronic acid. Matrix metalloproteinase (MMP) sensitive hyaluronic acid-based hydrogels were prepared by conjugation with two different peptides: cell adhesion peptides containing integrin binding domains (Arg-Gly-Asp: RGD) and a cross-linker with MMP degradable peptides to mimic the remodeling characteristics of natural extracellular matrices (ECMs) by cell-derived MMPs. Mechanical properties of these hydrogels were evaluated with different molecular weights of acrylated hyaluronic acid (10 kDa and 50 kDa) cross-linked by MMP sensitive peptides by measuring elastic modulus, viscous modulus, swelling ratio and degradation rate. The MMP sensitive hydrogel based on the 50 kDa hyaluronic acid showed a 31.5-fold shorter gelation time, 4.7-fold higher storage modulus and 0.51-fold smaller swelling ratio than those of the hydrogel based on the 10 kDa. Degradation rate was dependent on MMP sensitivity of the peptide cross-linker. MMP sensitive hyaluronic acid based hydrogels were degraded faster than MMP insensitive-hyaluronic acid-based hydrogels. Human mesenchymal stem cells (MSCs) were cultured in MMP-sensitive or insensitive hyaluronic acid-based hydrogels (50 kDa hyaluronic acid) and/or immobilized cell adhesive RGD peptides. Cells cultured in the MMP-sensitive hydrogel with RGD peptides showed dramatic cell spreading compared with that of the control, which remained round. This MMP-sensitive low molecular weight hyaluronic acid-based hydrogel could be useful in tissue engineering by improving tissue defect regeneration and tissue remodeling.