Synthesis and Characterization of Poly Styrene-Co-Poly 2-Hydroxyethylmethacrylate (HEMA) Copolymer and an Investigation of Free-Radical Copolymerization Propagation Kinetics by Solvent Effects

A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.

Synthesis of Comblike Poly(methyl methacrylate) by Atom Transfer Radical Polymerization with Poly(ethyl 2-bromoacrylate) as Macroinitiator

Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.

Injectable bioactive polymethyl methacrylate-hydrogel hybrid bone cement loaded with BMP-2 to improve osteogenesis for percutaneous vertebroplasty and kyphoplasty

Poly methyl methacrylate(PMMA)bone cement is used in augmenting and stabilizing fractured vertebral bodies through percutaneous vertebroplasty(PVP)and percutaneous kyphoplasty(PKP).However,applications of PMMA bone cement are limited by the high elasticity modulus of PMMA,its low biodegradability,and its limited ability to regenerate bone.To improve PMMA bio activity and biodegradability and to modify its elasticity modulus,we mixed PMMA bone cement with oxidized hyaluronic acid and carboxymethyl chitosan in situ cross-linking hydrogel loaded with bone morphogenetic protein-2(BMP-2)to achieve novel hybrid cement.These fabric ated PMMA-hydrogel hybrid cements exhibited lower setting temperatures,a lower elasticity modulus,and better biodegradability and biocompatibility than that of pure PMMA cement,while retaining acceptable setting times,mechanical strength,and inj ectability.In addition,we detected release of BMP-2 from the PMMA-hydrogel hybrid cements,significantly enhancing in vitro osteogenesis of bone marrow mesenchymal stem cells by up-regulating the gene expression of Runx2,Coll,and OPN.Use of PMMA-hydrogel hybrid cements loaded with BMP-2 on rabbit femoral condyle bone-defect models revealed their biodegradability and enhanced bone formation.Our study demonstrated the favorable mechanical properties,biocompatibility,and biodegradability of fabricated PMMA-hydrogel hybrid cements loaded with BMP-2,as well as their ability to improve osteogenesis,making them a promising material for use in PKP and PVP.

Porous alumina ceramic via gelcasting based on2-hydroxyethyl methacrylate dissolved in tert-butyl alcohol

To obtain porous alumina ceramic with high strength,a novel gelcasting system based on 2-hydroxyethyl methacrylate(HEMA)dissolved in tert-butyl alcohol(TBA)was developed.The polymerization of the HEMA-TBA gelcasting system,the thermal behavior of obtained green body,and the microstructures and mechanical properties of the sintered bodies were investigated by rheometer,TG-DSC,SEM and bending strength testing,respectively.The results show that,(1)10 mg/mL of the initiator(benzoyl peroxide)is the optimal amount for polymerization of this gelscasting system at 25 ℃;(2)The alumina suspension of the HEMA-TBA gelcasting system showing shear-thinning behavior is sufficiently low for gelcasting process;(3)The bending strength of porous alumina ceramic samples,whose porosities range from 42% to 56%,is from(8±0.5)to(91±4.5)MPa.

N-acetylcysteine and zinc sulphate abate di-2-ethylhexyl phthalate-mediated reproductive dysfunction in rats:Focus on oxidative and sex hormone receptors mechanisms

Objective:To investigate the potential of N-acetylcysteine(NAC)and zinc sulphate(ZnSO_(4))in mitigating reproductive dysfunction caused by di-2-ethylhexyl phthalate(DEHP)in rats and to understand the underlying mechanisms,specifically oxidative stress and sex hormone receptor activity.Methods:Thirty-five male Wistar rats were randomly divided into five equal groups(n=7 per group).Group 1 was administered 0.5 mL of distilled water and served as the control group.Group 2 was given only DEHP(750 mg/kg/day),while group 3,4 and 5 were given DEHP(750 mg/kg/day)plus NAC(100 mg/kg/day),DEHP(750 mg/kg/day)plus ZnSO_(4)(0.5 mg/kg/day),and DEHP(750 mg/kg/day)plus NAC(100 mg/kg/day)as well as ZnSO_(4)(0.5 mg/kg/day),respectively.All treatments lasted for 21 days.Samples were obtained after the rats were sacrificed,and hormones levels in the serum and markers of oxidative stress in the testicles were analyzed using the enzyme-linked immunosorbent assay.The amount of androgen receptors in the testicles was determined by immunohistochemistry,and the susceptibility of testosterone and DEHP to bind to androgen receptor and 5α-reductase was determined by molecular docking studies.Results:DEHP decreased reproductive hormones,testicular antioxidant enzymes,increased malondialdehyde levels,and negatively impacted histology of the pituitary and testes.NAC or ZnSO_(4) treatment showed a marked improvement in testicular antioxidant status and hormone levels,as well as a positive effect on the histology of the pituitary and testes.The combination of both treatments appeared to be more effective.The affinity of DEHP to bind to androgen receptors may lead to disruption of androgen receptor signaling,which can further result in dysfunction of hormones related to androgen.However,NAC is more likely to form stronger binding interactions with follicle stimulating hormone and luteinizing hormone receptors,as well as gonadotropin-releasing hormone receptors,when compared to DEHP.Conclusions:The possibility that NAC and ZnSO_(4) could downregulate DEHP-induced sex hormone changes is suggested by their potential to reduce toxicity.

Kinetic Study of Atom Transfer Radical Polymerization of 2-(N,N-Dimethylamino)ethyl Methacrylate

A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.

Grafting of 2-Hydroxyethyl Methacrylate onto Silk by Atom Transfer Radical Polymerization

Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.

Nonisothermal Kinetics of Free-Radical Polymerization of 2,2-Dinitropropyl Methacrylate

The 2,2-dinitropropyl methacrylate（DNPMA） was synthesized by esterification of α-methacrylic acid with 2,2-dinitropropanol.The free-radical bulk polymerization of DNPMA in the presence of 2,2-azobisisobutyronitrile（AIBN） was investigated by differential scanning calorimetry（DSC） in the nonisothermal mode.Kissinger,Ozawa and Barrett methods were applied to determine the activation energy（Ea） and the reaction order of the free-radical polymerization.The results showed that the temperature of exothermic polymerization peaks increased with increasing heating rate.With increasing the molar ratio of monomer/initiator and the heating rate,the reaction order of nonisothermal polymerization was approximately equal to 1.The average Ea value from Kissinger and Ozawa methods（77.74±1.07 kJ/mol） was smaller than the value from the Barrett method（Ea=102.36 kJ/mol）.

SYNTHESIS AND POLYMERIZATION OF TRI(2-PYRIDYL)METHYL METHACRYLATE

A novel methacrylate monomer with bulky side group, tri(2-pyridyl)methyl methacrylate (Tr2PyMA), was synthesized and polymerized. The polymer obtained by radical polymerization exhibits high isotactic tacticity.

A Novel Polymethyl Methacrylate (PMMA)-TiO_2 Nanocomposite and Its Thermal and Photic Stability

A new kind of polymethyl methacrylate （PMMA）-TiO2 nanocomposite was synthesized through polymerization. The thermal and photic stability of this PMMA TiO2 nanocomposites were investigated. The as prepared samples were characterized by scanning electron microscopy （SEM）, UV-Vis spectroscopy, differential thermal analysis （DTA） and the photo-induced weight loss, The results show that the photostability of the PMMA-TiO2 nanocomposite is higher than that of the pure PMMA under UV-light irradiation, The weight loss of the pure PMMA reaches 30 % after 300 h UVirradiation, while the composite only 0.3% under the identical experimental condition. The glass transition temperature （TR） of pure PMMA is only 80℃, while the Tg of the composite reaches 258℃. Compared with pure PMMA, the thermal stability of the composite is greatly enhanced.

Synthesis of Temperature- and pH-Sensitive Graft Copolymer Containing 2-(Diethylamino)ethyl Methacrylate and N-Vinylcaprolactam onto Silicone Rubber

Silicone rubber films were modified by the consecutive grafting of 2-(diethylamino)ethyl methacrylate (DEAEMA) and N-vinylcaprolactam (NVCL) using direct method on two steps with gamma-rays. The effect of absorbed dose and monomer concentration on grafting degree was determined. The grafted samples were verified by FTIR-ATR spectroscopy and swelling;thermal properties were analyzed by DSC and TGA. The stimuli-responsive behavior was studied by swelling and/or DSC. Thermo- and pH-sensitive films of (PP-g-DEAEMA)-g-NVCL presented a pH critical at 3.2 and LCST around 63.5℃.

THE EFFECTS OF N-2-HYDROXYETHYL-N-METHYL-p-TOLUIDINE ON METHYL METHACRYLATE RADICAL POLYMERI-ZATION AND ACRYLONITRILE PHOTOINDUCED POLYMERIZATION

The effects of N-2-hydroxyethyl-N-methyl-p-toluidine (HMT) on MMA polymerization using organic peroxide as an initiator and on AN photoinduced polymerization have been investigated respectively. The kinetics of polymerization and the overall activation energy of polymerization were determined. Based on kinetics study and the end group analysis of the polymer obtained by UV spectrum method, the initiation mechanism is proposed.

Ascorbic acid alleviates reproductive toxicity of di-(2-ethyl hexyl) phthalate in female Wistar rats

Objective:To investigate the potential of ascorbic acid in mitigating reproductive toxicity induced by di-(2-ethyl hexyl)phthalate(DEHP)in female Wistar rats,focusing on oxidative stress,hormone levels,and gonadotropin receptors expression.Methods:Forty female Wistar rats[30 days old,weighing(60±10)g]were randomly divided into five groups(n=8 per group).Group 1 received corn oil(control).Groups 2 and 3 were administered DEHP at 10 and 100 mg/kg body weight(b.wt.),respectively.Groups 4 and 5 received DEHP at 10 and 100 mg/kg b.wt.,respectively,plus ascorbic acid 100 mg/kg b.wt..All treatments were given orally for 30 days.Blood and ovarian tissues were collected to assess serum reproductive hormones,gonadotropin receptor gene expression,oxidative stress markers,and apoptosis.Results:DEHP,particularly at the higher dose,significantly decreased hormone levels(follicle-stimulating hormone,luteinizing hormone,estradiol)and gonadotropin receptor gene expression(FSHR,LHR),while increasing oxidative stress and apoptosis.Co-treatment with ascorbic acid significantly improved these parameters,reducing oxidative stress and apoptosis,and restoring hormone levels and gonadotropin receptor expression.Histopathology revealed fewer atretic follicles and less disruption in ovarian structure in DEHP and ascorbic acid-treated groups compared to those treated with DEHP alone.Conclusions:Ascorbic acid demonstrates protective effects against DEHP-induced reproductive toxicity in female rats,likely through mitigating oxidative stress and normalizing hormone levels and ovarian function.

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium

The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.

Glycerin Monostearate Aggravates Male Reproductive Toxicity Caused by Di(2-ethylhexyl)Phthalate in Rats

Human beings are increasingly exposed to phthalates,which are a group of chemicals used to make plastics more flexible and harder to break,and simultaneously ingesting abundant food emulsifiers via daily diet.The purpose of this study was to investigate the effect of the food emulsifier glycerin monostearate(GMS)on male reproductive toxicity caused by di(2-ethylhexyl)phthalate(DEHP,one of the phthalates)and explore the underlying mechanism.Thirty male Sprague-Dawley rats were randomly divided into control group,DEHP group and DEHP+GMS group.Rats in the DEHP group and DEHP+GMS group were orally administered with 200 mg/kg/d DEHP with or without 20 mg/kg/d GMS.After 30 days of continuous intervention,it was found that the serum testosterone level was significantly lowered in DEHP group and DEHP+GMS group than that in control group(P<0.01).The serum testosterone level and the relative testis weight were significantly decreased in the DEHP+GMS group as compared with those in the DEHP group and control group(P<0.05).More spermatids were observed to be shed off in DEHP+GMS group than in DEHP group.The expression levels of cell cycle checkpoint kinase 1(Chkl),cell division cycle gene 2(Cdc2),and cyclin-dependent kinase 2(CDK2)were down-regulated in DEHP group,and this tendency was more significant in DEHP+GMS group(P<0.05 or P<0.01).There was no significant difference in the P-glycoprotein(P-gp)expression between DEHP group and control group.However,P-gp was markedly down-regulated in DEHP+GMS group(P<O.Ol).The results indicated that the food emulsifier GMS aggravated the toxicity of DEHP on male reproduction by inhibiting the cell cycle of testicular cells and the expression of P-gp in testis tissues.

Reactive extraction for intensifying 2-ethylhexyl acrylate synthesis using deep eutectic solvent [Im:2PTSA]

2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.

Synergistic extraction of praseodymium with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline

The synergistic extraction of Pr^3＋ from hydrochloric medium using mixture of 2-ethylhexyl phosphonic acid mono- 2-ethylhexyl ester （P507, HL） and 8-Hydroxyquinoline （HQ） in heptane was investigated. The effect of equilibrium of aqueous acidity on extraction of Pr^3＋ was discussed. The effect of extractant concentraction, different diluents, equilibrium time and acetate ion concentration oil extraction reaction were also studied. With a method of double-logarithmic slope, composition of the extracted species on 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester and 8-Hydroxyquinoline was derived. The result shows that the synergistic extraction system not only overcomes emulsification of 8-Hydroxyquinoline, but also shows perfect capacity of synergistic extraction. The largest synergistic enhancement factor can be calculated to be 5.49 at pH 3.6 for Pr^3＋.

Solvent extraction equilibrium of dysprosium(Ⅲ) from nitric acid solutions with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester

In view of the importance of solvent extraction of rare earth metals with the acidic organophosphorous reagent,the development of a chemically based model applicable to high concentration is desired.In the present study,the equilibrium distribution of dysprosium(Ⅲ)between an aqueous nitric acid solution and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)was measured in the range of an initial aqueous dysprosium(Ⅲ)concentration from 1.0×10-3to 1.0×10-1kmol/m 3and PC88A concentration from 0.16 to 0.65 kmol/m3in Shellsol D70 as the diluent.The obtained data were analyzed using the chemically based model in order to correlate the equilibrium distribution ratios.In this model,dysprosium(Ⅲ)was assumed to be extracted with the PC88A dimer as a 1:3 complex,the activities were considered for the aqueous species,and the effective concentration of the PC88A dimer was calculated using Alstad's empirical equation.As a result,the apparent extraction equilibrium constant was determined to be 253(kmol·m- 3)-2with an excellent correlation between the experiment and calculation results in the wide range of the logarithm of the distribution ratio from-2 to 3.5.In conclusion,the methodology in this model would be effective for quantitative description of solvent extraction behavior of general rare earth elements as well as dysprosium.

Green tea polyphenols alleviate di-(2-ethylhexyl)phthalate-induced liver injury in mice

BACKGROUND Di(2-ethylhexyl)phthalate(DEHP)is a common plasticizer known to cause liver injury.Green tea is reported to exert therapeutic effects on heavy metal exposureinduced organ damage.However,limited studies have examined the therapeutic effects of green tea polyphenols(GTPs)on DEHP-induced liver damage.AIM To evaluate the molecular mechanism underlying the therapeutic effects of GTPs on DEHP-induced liver damage.METHODS C57BL/6J mice were divided into the following five groups:Control,model[DEHP(1500 mg/kg bodyweight)],treatment[DEHP(1500 mg/kg bodyweight)+GTP(70 mg/kg bodyweight),oil,and GTP(70 mg/kg bodyweight)]groups.After 8 wk,the liver function,blood lipid profile,and liver histopathology were examined.Differentially expressed micro RNAs(miRNAs)and mRNAs in the liver tissues were examined using high-throughput sequencing.Additionally,functional enrichment analysis and immune infiltration prediction were performed.The miRNA-mRNA regulatory axis was elucidated using the starBase database.Protein expression was evaluated using immunohistochemistry.RESULTS GTPs alleviated DHEP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,liver fibrosis,and mitochondrial and endoplasmic reticulum lesions in mice.The infiltration of macrophages,mast cells,and natural killer cells varied between the model and treatment groups.mmu-miR-141-3p(a differentially expressed miRNA),Zcchc24(a differentially expressed mRNA),and Zcchc24(a differentially expressed protein)constituted the miRNA-mRNA-protein regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage in mice.CONCLUSION This study demonstrated that GTPs mitigate DEHP-induced liver dysfunction,blood lipid dysregulation,fatty liver disease,and partial liver fibrosis,and regulate immune cell infiltration.Additionally,an important miRNAmRNA-protein molecular regulatory axis involved in mediating the therapeutic effects of GTPs on DEHP-induced liver damage was elucidated.

Synthesis of Highly-Selective Fibrous Adsorbent by Introducing 2-Ethylhexyl Hydrogen-2-Ethylhexylphosphonate for Scandium Adsorption

2-ethylhexyl hydrogen-2-ethylhexylphosphonate (EHEP) is commonly used as a metal extractant because it has a particular affinity for rare-earth metals like Scandium (Sc). To develop a highly-selective adsorbent of Sc(III), EHEP was introduced as a functional group onto a polyethylene fabric with radiation-induced graft polymerization(RIGP). The adsorption performances for Sc(III) were evaluated with aqueous solutions containing Sc(III) and Fe(III) in bath and column tests. As a result of column test, the adsorption capacities of Sc(III) and Fe(III) until the bed volume reached 5000 were 5.22 and 0.12 mg/g, respectively. It means that the amount of collected Sc(III) by the EHEP adsorbent was approximately 44 times higher than that of Fe(III). These results indicate that the grafted adsorbent containing EHEP has an extremely high selectivity for Sc(III) adsorption.