Phenolic-Based Chemical Production from Catalytic Depolymerization of Alkaline Lignin over Fumed Silica Catalyst

Lignin depolymerization into phenolic-based chemicals is an interesting process for utilizing and upgrading a benefit and value of lignin. In this study, the depolymerization reaction was performed to convert alkaline lignin into smaller molecule compounds. Fumed SiO₂ was used as a catalyst to improve catalytic activity in lignin decomposition. The important parameters in depolymerization process (i.e., reaction temperature, reaction time, etc.) were also investigated. In addition, gas chromatography with mass spectrometry (GC-MS), flame-ironized detector (GC-FID), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze and characterize the lignin products. It was found that fumed SiO₂ catalyst led the good catalytic activity in lignin depolymerization. The main products from catalytic depolymerization were guaiacol, syringol, vanillin, and phenols. Additionally, metal supported on fumed SiO₂ such as Cu/SiO₂ and Ni/SiO₂ increased the catalyst activity in terms of phenolic products yield.

Photopolymerization of Dimethacrylamide with (Meth)acrylates

A photopolymerizable dimethacrylamide was synthesized and copolymerized with the selected (meth)acrylates. The polymerization rate, degree of conversion, gel time, and compressive strength of the formed neat resins were investigated. The results show that in situ photo-polymerization of the synthesized dimethacrylamide with comonomers having an electron-withdrawing and/or acrylate group dramatically increased the polymerization rate, degree of conversion, and compressive strength. On the other hand, an electron-donating group on either carbon-carbon double bond or the ester linkage slowed down the polymerization. In contrast, the triethylene glycol dimethacrylate-based system did not show a clear pattern. Both strong hydrogen-bonding between (meth)acrylamide and organic acid groups may be responsible for higher compressive strengths. Within the limitation of this study, the photo-polymerization of dimethacrylamide can be greatly accelerated by copolymerization with monomers having electron-withdrawing and/or acrylate groups. The monomers with methacrylate group can significantly reduce the polymerization rate and degree of conversion.

The Role of Initiator in the Synthesis of Poly(Methyl Methacrylate)-Layered Silicate Nanocomposites through Bulk Polymerization

The structure-property relationship and initiator effect on bulk polymerized poly(methyl methacrylate) (PMMA)–oragnomodified layered silicate nanocomposites was investigated. In this study, we used 2, 2'-azobis (4-methoxy-2,4-dimethyl valeronitrile and benzoyl peroxide initiators for bulk polymerization. The bulk polymerized nanocomposites’ morphology was investigated by X-ray diffraction and transmission electron microscopy. The type of initiator strongly influences the physiochemical properties of the polymer nanocomposite. The thermal degradation of PMMA in the presence of nanofiller was studied. 5 wt% weight loss temperature (T5d) increased as compared to pure PMMA. The peak degradation temperature increased for the nanocomposites. Differential scanning calorimetry and dynamic mechanical analysis were performed to investigate the glass transition temperature and the nature of the constrained region as the reinforcement mechanism respectively. Furthermore, the optical properties such as UV-Vis and Total Luminous Transmission of nanocomposites are examined.

Biodegradable Cellulose-Based Materials for the Use in Food Packaging

Cellulose acetate (CA) is a natural biodegradable polymer. It forms transparent films by the casting technique. CA suffers from high degree of water permeability as well as the low thermal stability at high temperatures. To adjust the CA polymeric films to the manufacture of food packaging, its thermal and mechanical properties should be improved. The modification of CA by grafting it with N-Amino phenyl maleimide (N-APhM) led to the construction of hydrophobic branches throughout the polymeric matrix which reduced its wettability as compared to the parent CA. The branches built onto the polymeric chains had been characterized by UV/Vis, 13C-NMR and ESEM. The improvement of the thermal properties was investigated and compared to the parent CA using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), differential thermal analysis (DTA), contact angle and mechanical testing measurements. The results revealed that the water-uptake was reduced by increasing the graft percentage. The thermal and mechanical properties were also improved.

Preparation of Sorbent Materials for the Removal of Hardness and Organic Pollutants from Water and Wastewater

Ecological pollution is of great concern for human health and the environment. Numerous organic and inorganic pollutants usually discharged into the water caused carcinogenic or toxic effect for human and different life form. In this respect, this work aims to treat water contaminated by organic and inorganic waste using sorbent based on polystyrene. Therefore, two different series of adsorbent material were prepared; the first one included the preparation of polymeric sorbent from the reaction of styrene acrylate ester and alkyl acrylate. The second series involved syntheses of composite ion exchange resins of waste polystyrene and   amorphous carbon thin film (WPS/ACTF) by solvent evaporation using micro emulsion polymerization. The produced ACTF/WPS nanocomposite was sulfonated to produce cation exchange resins ACTF/WPSS nanocomposite. The sorbents of the first series were characterized using FTIR, 1H NMR, and gel permeation chromatography. The thermal properties of the cross-linked sorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The removal of organic pollutant was determined through absorption tests in a various organic solvent. The chemical and crystalline structure of nanocomposite of second series has been proven by studies of FTIR spectrum, X-rays, thermal analysis, SEM and TEM analysis to study morphology of resins and ACTF that assembled with polystyrene chain. It is found that the composite resins ACTF/WPSS are thermally stable and show higher chemical stability than ion exchange WPSS resins. The composite resin was evaluated for calcium hardness removal. The result is evident that the ACTF/WPSS composite has more prominent inorganic pollutant removal than WPSS resin. So, we recommend the using of nanocomposite resin as new potential applications for water treatment process.

Fabrication of Immune-Affinity Monolithic Array for Detection of α-Fetoprotein and Carcinoembryonic Antigen

In this paper, we presented a highly sensitive immune-affinity monolithic array for detection of α-fetoprotein (AFP) and carcinoembryonic antigen (CEA). Firstly, the epoxy functionalized monolith arrays were fabricated using UV initiated copolymerization method. Scanning electron microscopy (SEM) image showed that the poly(BABEA-co-GMA) monolith exhibited a well-controlled skeletal and well-distributed porous structure. Then, AFP and CEA immune-affinity monolithic arrays were prepared by immobilization of AFP and CEA antibodies on epoxy functionalized monolith arrays. With a non-competitive immune response format, the presented AFP and CEA immune-affinity arrays were demonstrated as an inexpensive, flexible, homogeneous and stable array for detection of AFP and CEA.

Chemical Characterization and Prebiotic Effect of Water-Soluble Polysaccharides from Zizyphus lotus Leaves

In order to investigate the prebiotic potential of oligosaccharides prepared by chemical hydrolysis of water-soluble polysaccharides (WSP) from Zizyphus lotus leaves, the effect of oligosaccharides on bacterial growth was studied. The chemical composition of WSP was evaluated by colorimetric assays revealed the average values: 7.05±0.73% proteins and 86.21±0.74% carbohydrates, among them 64.81±0.42% is neutral sugar and the rest 16.25±1.62% is uronic acids. The characterization of monosaccharides was determined by high performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) was found to be composed of galactose (23.95%), glucose (21.30%), rhamnose (20.28%), arabinose (9.55%), and glucuronic acid (22.95%). The effects of oligosaccharides on the growth of lactic acid bacteria were compared with those of fructooligosaccharide (RP95). The oligosaccharides concentration was 1g/L of Man, Rogosa, Sharpe broth. Bacterial growth was assessed during 2, 4.5, 6.5, 9, 12, 16 and 24 h by measuring the optical density of the cultures at 600 nm (OD600) and pH values. During fermentation, pH in broth cultures decreased from 6.7 to 5.87±0.15. The enumeration of lactic acid bacteria indicated that oligosaccharides led to a significant increase in bacteria (P≤0.05) compared to the control. The fermentative metabolism appeared to be faster on RP95 than on oligosaccharides from Zizyphus lotus leaves. Both RP95 and oligosaccharides showed clear prebiotic effects, but had differences in fermentation kinetics because of to the different degree of polymerization. This study shows the prebiotic effectiveness of oligosaccharides, and provides proof for the selection of leaves of Zizyphus lotus for use as functional food ingredients.

Development of a New Polymeric Material with Controlled Surface Micro-Morphology Aimed for Biosensors Applications

Compositions of different molar ratios of polymethylmethacrylate-co-methacrylic acid (PMMA-co-MAA) were synthesized via free-radical polymerization. Polymer coated surfaces have been produced on silicon wafers. Coated samples were analyzed by atomic force microscopy (AFM). The results have shown that the roughness of the surfaces have increased by increasing the molar ratio of monomer methacrylic acid (MAA). This study reveals that the gradual increase in surface roughness is due to the fact that carboxylic functional groups have been generated by MAA segments. Such surfaces can be desirable platforms for fabrication of the biosensors for detection of the viruses and diseases.

Heterophase Polymerization of Pyrrole and Thienyl End Capped Ethoxylated Nonyl Phenol by Iron (III) Chloride

This study presents synthesis of novel block copolymers of thienyl end capped ethoxylated nonyl phenol and pyrrole via chemical oxidative polymerization. Ethoxylated nonyl phenol (ENP) was reacted with 2-thiophenecarbonyl chloride in order to synthesize a macromonomer containing thienyl end-group (ENPThC). Then copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant. ENP-ThC served both as a macromonomer and an emulsifier for pyrrole with poor solubility in water. The synthesized block copolymers (ENP-ThC-b-PPy) were characterized by spectroscopic analysis and the electrical conductivities were investigated with 4-point probe technique.

Study on the Atomic-Oxygen-Protection Film Preparation of Organic Silicon and Its Properties

Materials used on exterior spacecraft surfaces are subjected to many environmental threats which can cause degradation, atomic oxygen is one of the most threats. We prepared organic silicon atomic-oxygen-protection film using method of polymerization. This paper presented the effects on the film structure and its durability of the preparation processing, and analyzed the polymerization theory, the film structure and composition of the film. At last, we tested the film in our ground based atomic oxygen simulator, and indicated that the film worked well.

Thermo-Sensitive Hydrogel: Control of Hydrophilic-Hydrophobic Transition

The study investigated the hydrophilic to hydrophobic transition of modified polyacrylamide hydrogel with the inclusion of N-isopropylacrylamide (NIAM). The modification was done by mimicking micellar polymerization, which resulted in better arrangement of NIAM chains in the polyacrylamide network. The degree of NIAM arrangement is described by NH number. The hydrophilic to hydrophobic transition was measured through the partition coefficient, K, of Orange II and Methylene Blue in hydrogel and in water. These dyes were chosen as a model for solutes with different degree of hydrophobicity. The study showed that the hydrogel with higher NH values resulted in better solubility of both dyes. Moreover, in temperature above the lower critical solution temperature (LCST) of Poly(N-isopropylacrylamide) (PNIAM)also caused the collapse of NIPAM chains which results in a more hydrophobic environment that increases the solubility of Methylene Blue and decreases the solubility of Orange II in the hydrogels with NIPAM present.

Modification and Characterization of Bacterial Cellulose Biopolymer as Proton Conducting Membrane

This study describes the preparation of a novel proton conducting membranes based on bacterial cellulose (BC) modified by grafting of 2-acrylamido-2-methyl-1 -propanesulfonic acid (AMPS) through UV-induced graft polymerization. These AMPS-g-BC membranes have been characterized by various techniques including FTIR, SEM and TGA, to find their successful grafting of AMPS on BC, surface morphology and thermal stability, respectively. Physical properties of AMPS-g-BC membranes have been assessed in terms of Lamda value( λ ), ion exchange capacity(IEC) and proton conductivity. The relationship between degree of grafting and AMPS concentration used for grafting has been determined by weight gain method. An optimum proton conductivity equal to 2.89x10-2 S cm-1 and IEC value equal to 1.79 mmol g-1 have been obtained when 20 wt% AMPS concentration is used for grafting (i.e. the corresponding membrane is notated as AMPS20-g-BC).

Universal Kinetic Modeling of RAFT Polymerization using Moment Equations

In the following text, we show that by introducing universal kinetic scheme, the origin of rate retardation and inhibition period which observed in dithiobenzoate-mediated RAFT polymerization can be described properly. We develop our model by utilizing the method of moments, then we apply our model to different monomer/RAFT agent systems, both homo- and copolymerization. The modeling results are in an excellent agreement with experiments and imply the validity of universal kinetic scheme, not only for dithiobenzoate-mediated systems, but also for different types of monomer/RAFT agent ones.

Novel Glycopolymers Containing Carbohydrate Moiety: Copolymerization and Thermal Properties

Polymers are one of the most widely used materials in our every day life. The subject of renewable resources has attracted great attention in the last period of time. New polymeric materials derived from renewable resources, like carbohydrates draw attention to public eye especially because of their biocompatibility and biodegradability. The aim of our paper was to obtain environmentally compatible polymers from monosaccharides. Novel glycopolymers based on D-glucose have been obtained from copolymerization of a new monomer carrying carbohydrate moiety with methyl methacrylate (MMA) via free radical bulk polymerization. Differential scanning calorimetry (DSC) was performed in order to study the copolymerization process of the monomer into the chosen co-monomer; the activation energy of this process was evaluated using Ozawa method. The copolymers obtained were characterized using ATR-FTIR spectroscopy. The thermal stability of the obtained products was studied by thermogravimetry (TG).

Realignment of f-actin Cytoskeleton in Osteocytes after Mechanical Loading

F-actin fibrils are the cytoskeleton of osteocytes. They react in a dynamic manner to mechanical loading, and strength and reposition their efforts to reinforce the cells structure. We hypothesize that f-actin is temporarly disrupted after loading and repolymerizes in a new orientation to oppose the applied load. In vitro studies are conducted to determine f-actin disruption after varying mechanical stimulus parameters that are known to affect bone formation. Results indicate that the f-actin cytoskeleton is disrupted in vitro as a function of applied mechanical stimulus parameters and that the f-actin bundles reassemble after loading induced disruption within 3 minutes after cessation of loading. The disruption of the factin cytoskeleton depends on the magnitude of stretch, the numbers of loading cycles, frequency, the insertion of rest between loading cycles and extracellular calcium. In vivo studies also demonstrate disruption of the f-actin cytoskeleton in cells embedded in the bone matrix immediately after mechanical loading. These studies suggest that adaptation of the f-actin fiber bundles of the cytoskeleton in response to applied loads occurs by disruption and subsequent repolymerization.