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There is a pressing need around the world to develop novel functional biodegradable materials to separate oil/water mixtures and emulsions completely. Recently, superhydrophilicity and underwater superoleophobicity materials have been attracted attention due to their high efficiency in oil/water separation. However, it is still a challenge to prepare materials that combine oil/water separation and water purification in an environment-friendly way. In this work, biodegradable starch-based nanospheres (SNPs) coated filter paper was prepared in a low-cost, simple, and environmentally friendly manner. The SNPs coating could not only help to change the wettability of the substrate material but also build the hierarchical micro and nano structures which are conducive to separation and purification process. After modification by coating SNPs, the filter paper exhibited excellent performance in a wide range of oil/water mixtures or emulsions separation and the wettability of the filter paper could be regulated by adjusting the pH value. The modified filter paper presented good recyclability after several separation process. Furthermore, the as-prepared filter paper could also remove water-soluble contaminants during the oil/water separation process, thus realizing to combine separation and purification process in one single step. This biodegradable starch-based separating material with good separation performance, stability and recyclability has significant application potential in practical separation and purification process.

Pickering high internal phase emulsions (HIPEs) stabilized solely by bioderived starch-based particles hold potential for application in the food and pharmaceutical fields. This paper reports the use of a thermoresponsive 2-hydroxy-3-butoxypropyl starch (HBPS) particle as a representative natural biocompatible material for use as an effective stabilizer for HIPE formation. HBPS is synthesized by using butyl glycidyl ether as a hydrophobic reagent to change the hydrophobic–hydrophilic balance of starch, and then starch-based particles are fabricated by a simple nanoprecipitation procedure. The size of particles increased with an increase in temperature, and the particles are essentially monodisperse with a PDI of about 0.1 when the temperature was above 15 °C. These HBPS particles were subsequently used as an effective stabilizer to fabricate stable oil-in-water (o/w) Pickering HIPEs with an internal phase volume of 80% at different stabilizer concentrations. The results demonstrated that increasing the particle concentration is conducive to the formation of stable Pickering HIPEs with greater stiffnesses. In addition, the nutraceutical material (β-carotene) was encapsulated into HIPEs and in vitro release experiments revealed that the release in this system can be controlled by adjusting the temperature.

To realize intelligent and low-cost protective materials, the development of compounds with smart stress-responsive properties and self-healing abilities over a wide temperature range is a major research goal. In this study, a series of impact hardening polymers (IHPs) with stress-responsive properties and self-healing ability in low temperature were synthesized via the condensation copolymerization of silicone polymers with various chain lengths and boron contents. The results of rheological analysis indicate that the IHPs have self-healing ability at low temperatures (healing times of less than 30 h and healing efficiencies better than 80% at −25 °C). Moreover, the relative shear stiffening effect (RSTe), which describes the stress-responsive ability of the IHP, exceeded 2000. In addition, the self-healing mechanism of IHP was investigated by Fourier transform infrared spectroscopy microscopy and pulsed 1H-NMR measurements. The results suggested that reversible dynamic cross-linking arising from the boron compound and the reduction in the threshold entanglement density owing to the longer length of the flexible polymeric backbone is crucial to impart low-temperature self-healing ability and stress-responsive properties to IHP.

Inverse Pickering emulsions stabilized by naturally derived particles are of interesting during the past decade. In this study, starch-based nanoparticles were used as a particulate emulsifier to stabilize a w/o Pickering emulsion. The effects of particle concentration and oil volume fraction on the emulsion type and stability were investigated in detail. Catastrophic phase inversion from o/w to w/o emulsions occurred at a volume fraction of oil of 0.3-0.4, without altering the particle wettability. Further, a linear relation existed between the average droplet diameter and total amounts of starch-based nanoparticles. The obtained starch-based nanoparticles also served as a Pickering stabilizer to conduct a w/o Pickering polymerization. Raspberry-like thermoresponsive starch-poly(N-isopropyl acrylamide) nanocomposites with a well-defined structure were synthesized.

Nonspherical colloidal particles with various geometries and different compositions have attracted tremendous attention and been widely researched. The preparation of polymer colloidal particles with controlled shapes by seeded polymerization is recognized as the most promising technique owing to the precise control of various morphologies and using non-cross-linked seed particles are of particular interest. Seeds particles derived from natural biopolymers are seldom applied. Hence, non-cross-linked starch-based seed could be used to fabricate the anisotropic particles by soap-free seed polymerization. Non-cross-linked starch-based seed particles were prepared by a nanoprecipitation method. Starch/polystyrene composite colloidal particles with shape-tunable were fabricated by soap-free seeded polymerization using starch-based seed. The effect of the polymerization time, monomer feed ratio and seed type were investigated. The seed particles with a single- or multi-hole structure were obtained after swelling with styrene. The resulting particles including golf-like, raspberry-like, octahedron-like and snowman-like structures, was fabricated on the polymerization process. This study firstly reports that the morphology of composite particles from golf-like to snowman-like at high monomer feed ratio using starch-based seed. At low monomer feed ratio, raspberry-like particles were obtained by surface nucleation increasing process. In addition, seed type also effect the morphology of composite particles.

Surface wettability, one of the most important parameters for oil–water separation, depends on the chemical composition and surface roughness of a material. Herein, the Pickering emulsion template method is proposed to control the surface wettability of polymer microspheres. Upon the dispersion of modified diatomite particles in the aqueous phase, a superhydrophobic surface was formed on the polymer microspheres via Pickering emulsion polymerization, with a water contact angle of 152°. When the initial dispersion location of the modified diatomite particles changed from water to oil, a hydrophilic/underwater superoleophilic surface with micro/nanoscale hierarchical structures formed on the polymer microspheres. This special wettability enabled the microsphere layer to serve as an adsorbent with underwater superoleophilicity, achieving efficient oil separation from various oil-in-water emulsions with high separation efficiency of >99.8%. Hence, this study provides a valuable strategy based on the Pickering emulsion template method to design materials with special wettability for realizing promising emulsion separation.

Stable water-in-oil (W/O) emulsions can produce at many industrial production occasions. However, most materials for its separation have serious fouling problems. To overcome this shortcoming, we fabricated an easy cleaning multifunctional starch-based material with unique wetting behavior which could realize efficient separation and purification of W/O emulsions. This material has a hierarchical structure and superoleophilic and under oil superhydrophobic surfaces which could separate various W/O emulsions in a high separation efficiency and flux without external pressure. In addition, the decrease of separation flux was not observed for this material, which can be reused more than 10 times after washing with ethanol and drying after each separation cycle. Furthermore, this material also could realize efficient removal of dyes and heavy-metal and rare-earth ions simultaneously during a separation process. The material shows great potential for separating and purifying stable W/O emulsions produced during the industrial production.

A series of chemically cross-linked microgel composite hydrogels (MCH gels) with excellent toughness and stretchability were prepared using core–shell polymer microspheres as cross-linking junctions. In our strategy, MCH gels are obtained by connecting microspheres with polyacrylamide (PAAm) chains chemically grafted onto their surfaces, where an organic cross-linking agent is completely unnecessary. The mechanical behavior of the MCH gels was analyzed, and superresolution fluorescence microscopy and scanning electron microscopy were used to investigate their toughening mechanism. The results indicated that the homogeneous network structure resulting from the good compatibility between the core–shell microspheres and matrix was an important reason for the excellent toughness of the MCH gels. In addition to interactions among H bonds in the grafted PAAm chains, reversible deformation of the core–shell microspheres acting as cross-linking junctions, which arises from the flexibility of the microspheres, and the effect of cavitation between the microspheres and matrix could also effectively dissipate energy during deformation of the MCH gels.

The biodegradable polysaccharide hydrogels have attracted much attention due to its biocompatible and non-toxicity. Herein, we report a starch hydrogel synthesized via thiol-ene click reaction between thiol starch (St-SH) and allyl starch (AS). The swelling behaviors, rheological experiment and biodegradable properties of the obtained hydrogel were investigated in details. The chemical structure of functioned starch was confirmed by 1 H-NMR and 13 C-NMR. Moreover, the rheological experiment indicated that starch hydrogel possessed high mechanical strength, and its modulus could be manipulated by the thiol-ene molar ratio. Biodegradation tests revealed that the hydrogel could be biodegradable rapidly in the presence of α-amylase. The biodegradation rate could be controlled by the thiol-ene molar ratio or the concentration of α-amylase. Degradation kinetics from the hydrogel suggested that the degradation/erosion of starch hydrogel come from a combination of both the surface erosion and diffusion mechanisms.

The convenient synthesis of core-shell nanoparticles containing degradable components is very desirable given the potential applications of such nanoparticles in biomaterials. A facile approach for producing monodisperse starch-polystyrene nanocomposites with well-defined core-shell structures in the absence of a surfactant was developed. The initially-formed Pickering emulsions underwent conversion into seeded emulsions during the polymerization, wherein the amphiphilic starch-based nanospheres (SNPs) serve as stabilizer and seed. A possible mechanism for this transition was explored based on the morphology and size variations of the emulsion droplets and the resultant nanospheres. The effects of the monomer concentration, SNP content and size, and pH on the core-shell nanospheres were investigated. With increasing monomer concentration, the core size of the particles remained almost unchanged, while the shell layer thickness increased almost linearly. The size of the core-shell nanospheres can be regulated by adjusting the pH and the SNP content and size.

Using a facile two-step method, the researchers synthesized a pH-responsive double-network (DN) hydrogel with high strength and toughness, consisting of a B(OH)4− linked hydroxypropyl guar gum (HPG) network and a covalently cross-linked polyacrylamide (PAAm) network. The mechanical strength of HPG/PAAm DN gel was investigated as a function of synthesis conditions, HPG content, sodium borate concentration and soaking time. The resulting DN gel exhibited unique pH-responsive properties and excellent mechanical properties, with a fracture stress of 843 kPa, and an excellent extensibility of 1400% (12−14 times its initial length). The relationship between mechanical property and the synergy of HPG and PAAm networks was discussed systematically. The DN gel possessed self-recovery under small deformation, but displayed self-reinforcement under large deformation.

Although lots of impact protective materials reported exhibited better impact protective performance thanking to their excellent mechanical performance, their applications were still seriously impeded due to absence of soft–stiffness switch smartness. Herein, a novel impact hardening polymer (IHP) with negative Poisson's ratio was synthesized via a condensation polymerization, followed by a simple thermal annealing to achieve a perfect soft–stiffness switch characteristic and self-healing capacity. Its soft–stiffness switch ability σ , defined as G ′ max / G ′ min in rheological analysis, can reach 9000, which is never reported so far. The result of laser speckle scatter measurement elucidates that IHP has negative Poisson's ratio, which is the root cause why IHP exhibits soft–stiffness switch capacity. Finally, 3D composite anti-impact fabrics were prepared by dip–coating IHP dispersion onto a 3D porous polyester fabric. Not only the impact protective performance of anti-impact fabrics finished with the IHP is significantly improved, but also the flexibility and hand feeling of anti-impact fabrics finished with the IHP are obviously very good because the IHP is flexible without impact.

Conventional approaches to generating double emulsions are cumbersome, complicated, and based on a two-step emulsification process using a combination of two distinctive surfactants. In this work, the surface properties of diatomite particles were successfully tailored by chemical modification with palmitoyl chloride. The properties of the resulting diatomite particles changed from the original hydrophilicity to hydrophobicity, leading to straightforward stabilization of oil-in-water-in-oil (O/W/O) Pickering double emulsions by a one-step emulsification process. Pickering double high internal phase emulsions (HIPEs) with an internal phase up to 80 vol% could be produced solely using the modified diatomite particles. The water-in-oil (W/O) droplet sizes of these HIPEs were much larger than the droplets of conventional nanoparticle-stabilized Pickering HIPEs. Furthermore, using the O/W/O Pickering double emulsions as templates, the porous polymer particles were fabricated. In addition, it was demonstrated that the wide particle size distribution of diatomite particles and modified heterogeneity were the reasons for the formation of multiple emulsions.

Conventional hydrogels freeze and harden at sub-zero temperatures and their mechanical properties are considerably inadequate for practical load-bearing applications. These drawbacks hinder their application possibilities. In this work, we propose a new strategy based on Pickering emulsion polymerization to fabricate novel organohydrogels with antifreeze properties. Ethylene glycol (EG) is introduced into the aqueous phase of the Pickering high internal phase emulsion (HIPE) to effectively inhibit water from freezing. The resulting bicontinuous organohydrogels are prepared through simultaneous polymerization in the external and internal phases to provide enhanced mechanical properties and good hydrophilic-oleophilic properties. Furthermore, the organohydrogels are more stable than conventional hydrogels under ambient conditions and remain unfrozen and mechanically flexible down to −40 °C.

Polysaccharide-based hydrogels are remarkable materials for the biomedical fields because of its excellent biodegradation and biocompatibility. In this work, a novel polysaccharide-based hydrogel was fabricated by in situ crosslinking of starch-based nanoparticles and polyvinylamine. Starch was decorated with cholesterol group and aldehyde groups. TEM and DLS showed that the cholesterol modified oxidation starch (OCS) exhibited a core-shell nanoparticles with mean size of ∼143 nm in aqueous. The hydrogel was then synthesized via Schiff base reaction. Rheological measurements demonstrated the incorporation of cholesterol groups not only reduced the gel time but also improved the storage modulus of the hydrogel compared with the oxide starch crosslinked hydrogel. SEM showed the OCS based hydrogels possess a well-defined porous structure. Furthermore, doxorubicin (DOX) was used as model drug to investigate the control and release properties of OCS hydrogels. This OCS hydrogel would be a promising drug carrier for biomedical applications.

Emulsions stabilized solely by edible particles have attracted great interest very recently because of their potential application in the food and pharmaceutical fields. In this work, starch-based nanospheres are used as the particulate emulsifier for triglyceride–water emulsions. The effects of particle concentration, oil:water ratio and salt concentration on emulsion type and stability are investigated in detail. The linear relationship between the inverse average oil drop diameter and the particle concentration allows estimation of the coverage by particles of the curved oil–water interfaces. Confocal microscopy confirms that the nanospheres are mainly adsorbed at the liquid interface to form a dense film around the dispersed drops impeding coalescence. Moreover, catastrophic phase inversion from oil-in-water (O/W) to water-in-oil (W/O) emulsions is achieved by increasing the volume fraction of oil beyond 0.65. The stability to creaming of O/W emulsions increases approaching phase inversion, as does the stability to sedimentation of W/O emulsions. Finally, O/W emulsions are destabilized with respect to coalescence on adding salt.

Biodegradable thermosensitive hydrogels have attracted great interest because of their potential in biomedical applications. Herein, we present a novel, thermoresponsive poly(2-(2-methoxyethoxy)ethyl methacrylate) hydrogels with starch-based nanospheres as cross-linkers (NMH). NMHs exhibit a narrow lower critical phase transition temperature (LCST) range and high mechanical strength compared with conventional, small molecular cross-linked hydrogels (CMH). Fourier transform infrared (FT-IR) spectroscopy confirms that the NMHs are degradable in aqueous medium. The phase transition temperature of the NMHs is ∼4 °C compared with ∼25 °C for CMH. The NMHs can sustain strength of 12.2 MPa, 10 times more than that of CMH. Moreover, the deswelling rate of NMHs is faster than CMH. The different concentrations of nanospheres can efficiently regulate the various properties of NMHs. The NMHs have excellent properties because of its even network structure formed by nanosphere cross-linkers.

High strength, stimuli-responsive poly(acrylamide) composite hydrogels (PAAm CH gels) were prepared by grafting polymerization of acrylamide (AAm) onto temperature-sensitive core–shell microgels. These microgels, composing of poly(N-isopropylacrylamide) as core and polyvinylamine (PVAm) as shell, were used as both initiator and crosslinker to form a robust three-dimensional network via bonding the poly(acrylamide) (PAAm) backbone. The CH gels exhibited a remarkably rapid shrinking rate and transmittance switch in response to the environmental temperature change, which the conventional chemically cross-linking PAAm hydrogels (PAAm OR) were short of. Even compared to the bulk PNIPAAm hydrogels (PNIPAAm OR) crosslinked with N,N′-methylenebisacrylamide (MBA), the CH gels were featured with faster responsive rate, which could be attributed to the formation of interconnected water transportation channels between the microspheres and PAAm gel matrix due to the fast shrinking of microgels. Moreover, the effects of microgel species and content on swelling and mechanical properties of CH gels were also systematically investigated. The results elaborated that the CH gels could be compressed almost 99% without breaking and completely recovered their original shape when the stress was removed. And the optimized compressive strength of CH gels could be up to 21.94 MPa. Based on the analysis of CH gel mechanical properties, the influence of microsphere content on effective network chains density of CH gels was discussed through rheology measurements. Finally, the essential reinforcement on mechanical properties was mainly contributed to the homogeneous microstructure of hydrogel network and the energy dissipation mechanism of microgels in gel matrix.

A cationic surfactant monomer, dimethyldodecy1(2-acrylamidoethypammonium bromide (AMQC(12)) was synthesized. A family of hydrophobic-associating cross-linking hydrogels (HAC-gels) fabricated via the self-assembly of amphiphilic multiblock copolymers of acrylamide and AMQC-12 can be synthesized by free-radical aqueous solution micelle copolymerization in the absence of surfactants using the one-pot method. The HAC-gels possessed outstanding mechanical performance, with optimal tensile strength, compressive strength, and elongation at break of 250 kPa, 14 MPa, and 1850%, respectively. Meanwhile, the HAC-gels exhibited self-healing property, and tetrahydrofuran (THF) significantly accelerated their self-healing process. The recovery hysteresis of hydrophobic-associating hydrogels prepared in the presence of surfactants can be eliminated because of homogeneity of the hydrogel network and the dynamic and mobile properties of physical cross-linking junctions. Investigations on the mechanical property and structure evolution of hydrogels revealed that the hydrophobic-associating interaction was the driving force of self-assembly of amphiphilic multiblock copolymers. Furthermore, spherical micelles and macroscopic cross-linking network can be easily switched reversibly by regulating copolymers concentration. (C) 2013 Elsevier Ltd. All rights reserved.

Two macrocyclic chelating MRI agents (Gd-DO3A)(3)-TAB and (Gd-DO3A)(2)-DAB have been successfully synthesized by appending three and two Gd-DO3A moieties upon the acetylbenzene derivatives, respectively. The longitudinal relaxivity of (Gd-DO3A)(3)-TAB measured at 20 MHz, 37 degrees C and pH 7.0 is 6.1 mMGd(-1) s(-1), 74% higher than that of the mononuclear clinical agent [Gd(DOTA)(H2O)]. A 30% or 16% increase in relaxivity was observed upon addition of 0.72 mMbovine serum albumin (BSA) or 10-fold of diamagnetic ion La3+. More importantly, the thermodynamic stability and kinetic inertness of (GdDO3A)(3)-TAB are comparable to or better than that of [Gd(DTPA)(H2O)](2). The luminescence lifetime study on the corresponding (Eu-DO3A)3-TAB analog demonstrated that the agent had one inner-sphere water coordinated to the Eu3+ center within the complex. The cytotoxicity study indicated that the toxicity of the agent was low with IC50 = 18 mM. In addition, the characterization of its dinuclear analog (GdDO3A)(2)-DAB has also been investigated. (C) 2013 Elsevier B.V. All rights reserved.

Starch is successively modified by acetic anhydride and phthalic anhydride, and then starch-based nanospheres are fabricated by a simple nanoprecipitation procedure. These pH-responsive amphiphilic starch-based nanospheres of uniform size are used as particulate emulsifiers to stabilize Pickering emulsions. CLSM and SEM characterization find that starch-based nanospheres adsorbed at the interface between oil phase and water phase. Moreover, the catastrophic inversion and transitional inversion of such emulsions can be easily achieved by varied the water/oil volume ratio and pH of aqueous dispersion, respectively.

Fluorescein isothiocyanate (FITC) is covalently attached onto the starch acetate, and the fluorescein-labeled starch acetate can self-assemble to form uniform nanospheres in water. The size of the fluorescent nanospheres can be easily controlled by adjusting the polymer concentration in acetone and the proportions of the water and organic phases. The fluorescent intensity of the nanospheres increases with increasing pH, and its fluorescent intensity has no major effect in the physiologically relevant range from pH 5.7 to pH 8 compared with free FITC. Fluorescence quenching studies prove that the fluorescent nanospheres showed a super fluorescent stability without self-association. The fluorescent nanospheres are degradable and can be potential applied for pH-sensing in biological samples.

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of PVA aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug. The drug release followed different release mechanism at pH 4.0 and pH 7.4, respectively.

Acetylated corn starches with different degrees of substitution (DS 0.85, DS 1.78, DS 2.89) were synthesized by the reaction of corn starch with acetic anhydride in the presence of acetic acid under varying reaction temperatures. The product was characterized by FTIR spectroscopy, 1 H NMR, X-ray diffraction and contact angle measurement. Acid-base titration and 1 H NMR methods were employed to determine the degree of substitution of product. FTIR spectroscopic analysis showed that the characteristic absorption intensities of esterified starch increased with increase in the degree of substitution, and the characterized peak of hydroxyl group almost disappeared in the spectrum of DS 2.89 acetylated starch. The detailed chemical microstructure of native starch and acetylated starch was confirmed by 1 H NMR, 13 C NMR and 13 C– 1 H COSY spectra. Analysis of 1 H NMR spectra of acetylated starches was assigned accurately. Strong peaks in X-ray diffraction of acetylated starch revealed that new crystalline regions were formed. Compared with native starch, the hydrophobic performance of acetylated starch esters was increased. The contact angle of acetylated starch with DS 2.89 was 68.2°.

Two series of the nanocomposite hydrogels were synthesized by in-situ solution polymerization. One pre-gel solution was obtained by directly dispersing the montmorillonite (MMT) powder into aqueous monomer solution and the other pre-gel solution was obtained by mixing monomer aqueous solution and the dispersion of MMT. The structure and performance of two series of hydrogels in dry state were studied by XRD, Raman spectroscopy, TEM and Al-27 MAS NMR. Compressing test results showed that the gel strength of the hydrogels prepared by the latter method was much higher than that by the former method. When acryloyloxyethyl trimethyl ammonium chloride (DAC) was introduced into the system, hydrogels with excellent nanostructure could be synthesized. The result of Al-27 MAS NMR suggested that the chemical environment of aluminum in MMT was changed by the introduction of DAC due to the interaction between the groups of DAC and MMT layers. Thus, the combination of copolymerizing with strong polar monomers and using the dispersion of MMT were the effective ways to obtain tranocomposite hydrogel of MMT and ionic monomers. The nanostructure of the hydrogel improved the gel strength, while the swelling ratio of the hydrogel depended on synergic effects of multifunctional groups.

A series of novel polyampholyte superabsorbent nanocomposites with excellent gel strength were synthesized by in situ solution polymerization in aqueous solution. Acrylic acid and acryloyloxyethyl trimethyl ammonium chloride (DAC) were employed as ionic monomers and montmorillonite (MMT) was used as inorganic component. The addition of cationic component could supply the positive charge in the network of nanocomposite and promote the formation of nanostructure of composites due to the interaction between DAC and clay platelets. The performance of polyampholyte nanocomposites were investigated and the result showed that the gel strength of nanocomposite hydrogel in distilled water and 0.9 wt% NaCl solution could reach 198.85 and 204.23 mJ/g, respectively, which were 13 times of the gel strength of matrix. The investigation of swelling behaviors showed that the nanocomposites had particular swelling behaviors of polyampholytes hydrogel in solution with different pH values and concentration of NaCl.

High-solids, low-viscosity, stable poly(acrylamide-co-acrylic acid) aqueous latex dispersions were prepared by the dispersion polymerization of acrylamide (AM) and acrylic acid (AA) in an aqueous solution of ammonium sulfate (AS) medium using anionic polyelectrolytes as stabilizers. The anionic polyelectrolytes employed include poly(2-acrylamido-2-methylpropanesulfonic acid sodium) (PAMPSNa) homopolymer and random copolymers of 2-acrylamido-2-methylpropanesulfonic acid sodium (AMPSNa) with methacrylic acid sodium (MAANa), acrylic acid sodium (AANa) or acrylamide (AM). The influences of stabilizer's structure, composition, molecular weight and concentration, AA/AM molar feed ratio, total monomer, initiator and aqueous solution of AS concentration, and stirring speed on the monomer conversion, the particle size and distribution, the bulk viscosity and stability of the dispersions, and the intrinsic viscosity of the resulting copolymer were systematically investigated. Polydisperse spherical as well as ellipsoidal particles were formed in the system. The broad particle size distributions indicated that coalescence of the particles takes place to a greater extent. The chemical structures of the final formed copolymers were characterized by FTIR and 13C NMR. The result obtained by 13C NMR was excellent agreement between the feed monomer compositions and the final copolymer compositions.

Dodecenly succinic anhydride (DDSA) starches were prepared commercially by the base catalyzed reaction of DDSA in pre-emulsion with starch granular in aqueous slurry. The results indicated that the degree of substitution and reaction efficiency were 0.0256% and 42.7%, respectively, at the parameters for the preparation of DDSA starches in starch slurry 30%, DDSA/starch radio 10% (wt/wt), pH 8.5–9.0, reaction temperature 313 K. After modification, product surface chemical composite had been changed which was prone to migrate into less polar solution. The chemical structural characteristics were investigated by methods of FTIR and 1 H NMR. The results of X-ray diffraction showed the native A-type crystalline pattern, indicating that reaction of corn starch with DDSA caused no change in the crystalline structure. Compared to native starch, the hydrophobic performance of esters was greatly increased. With the DS increasing, contact angles were gradually increased, however, the adhesion works were decreased. The maximum contact angle of DDSA starch could attend to 123°, and the corresponding adhesion work was 33.2 mJ m −2 .

Dispersion copolymerization of acrylamide (AM) with 2-methylacryloylxyethyl trimethyl ammonium chloride (DMC) has been carried out in aqueous salts solution containing ammonium sulfate and sodium chloride with poly(acryloylxyethyl trimethyl ammonium chloride) (PDAC) as the stabilizer and 2,2'-azobis[2-(2-inidazolin-2-yl)propane]-dihydro chloride (VA-044) as the initiator. A new particle formation mechanism of the dispersion polymerization for the present system has been proposed. The effects of inorganic salts and stabilizer concentration on dispersion polymerization have been investigated. The results show that varying the salt concentration could affect the morphology and molecular weight of the resultant copolymer particles significantly. With increasing the stabilizer concentration, the particle size decreased at first and then increased, meanwhile the effect on the copolymer molecular weight was the contrary. These results had been rationalized based on the proposed mechanism.

The structure of hydrated poly(aspartic acid) sodium (PAANa) and in blended PAANa, which was blended with poly(vinyl alcohol) (PVA), is characterized by means of high-resolution solid-state 23Na NMR. There are two peaks in dried pure PAANa, which are assigned to associated ions (about −16 ppm) and isolated ions or end group ions of PAANa (7.2 ppm), respectively. With an increase in hydration, the 23Na chemical shifts of these two peaks are changed to tend toward 0 ppm, and the line width at half the height of the 23Na resonance decreases. In contrast, in the blended samples, the 23Na resonance shapes and chemical shift values are significantly changed depending on the ratio of the PAANa/PVA blends and the temperature. On the basis of these experimental results, the structure of the blends was elucidated.

Solid state 13 C CP/MAS NMR measurements have been carried out on poly(aspartic acid) sodium (PAANa)/poly(vinyl alcohol) (PVA) blends over a wide range of temperatures. From these experimental results, it is found that the main-chain conformations of PAANa in PAANa/PVA blends take the α -helix form over a wide range of blend ratios, and, in contrast, the conformation and dynamics of the side chains of PAANa are strongly influenced by the formation of an intermolecular hydrogen bond between the carboxyl group of the side chains and the hydroxyl group of PVA. The behavior of the proton spin–lattice relaxation times in the rotating frame ( T 1 ρ (H)) and the laboratory frame ( T 1 (H)) indicates that when the blend ratio of PAANa and PVA is 1:1, they are miscible.

High-resolution 13 C CP/MAS NMR and pulse 1 H NMR experiments were carried out for hydrated poly(aspartic acid) sodium salt, in order to investigate the conformation and molecular motion of the polymer. From these experimental results, it is found that the main-chain conformation of poly(aspartic acid) sodium salt which takes an α-helix form in the dry state is not drastically affected by an addition of water. In the 13 C CP/MAS NMR spectrum, a new peak at ca. 184 ppm appears, which comes from the formation of hydrogen bond between the carbonyl carbon of the side chains and water, and the intensity of the peak is associated with the water content. The 13 C spin-lattice relaxation time ( T 1 ) experiments show that the T 1 values for the individual carbons of the polymer are decreased with an increase in the water content. This shows that the mobility of the polymer is increased with an increase in the water content. Further, the 1 H spin-spin relaxation time ( T 2 ) experiments show that the polymer has the two or three components with different molecular motion. With an increase in the water content or temperature, the T 2 values of hydrated PAANa are increased. This shows that the molecular motion is increased. In the high water content, the polymer has a signal component in the molecular motion. This shows that the polymer is uniformly hydrated.

High-resolution 13C CP/MAS NMR spectra of poly(aspartic acid) (PAA) and its sodium salt (PAANa) obtained with various neutralization numbers, n (=[COONa]/[COOH+COONa], where [x] is the molar concentration of x), have been measured over a wide range of temperatures, in order to elucidate the conformation and its stability in the solid state. From these experimental results it was found that, at room temperature (25°C), the main chain of PAA takes a mixture of right-handed α (αR)-helix, ω-helix and β-sheet forms and, with an increase in temperature from 25°C to 180°C, changes from αR-helix form and ω-helix form to β-sheet forms. On the other hand, the main chain of PAANa takes the right-handed αR-helix form in the temperature range from 25°C to 210°C. With a decrease in the neutralization number, PAANa changes to PAA and the NMR spectra are correspondingly changed.