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Multicomponent hydrogels are an important class of materials that have unique properties which are exploited for target-specific applications in medicine. Although a few systems are currently in preclinical trials and clinical applications, the translation into commercial products is still in its infancy. This is due to the lack of partnership between academia and industry which is very important for scale-up and commercialization. This chapter briefly summarizes the toxicity issues of multicomponent hydrogels related to human health and the environment, which need to be addressed before discussing the regulatory aspects for clinical translation, commercialization and environmental mitigation. The types of approvals required and the factors affecting the scale-up and manufacturing processes are presented in this chapter.

In this study, a new multi-stimulus cationic copolymer hydrogel was developed by bulk photo-polymerization of N-acryloyl-N’-propyl piperazine (AcrNPP) and poly (ethylene glycol) methacrylate (PEGMA) with ethylene glycol dimethacrylate (EGDMA) as crosslinker. The effect of multiple external stimuli, concentration of monomers, and equilibrium swelling of the hydrogels was studied in detail. The gels swelled in acidic solutions due to protonation of tertiary amine in the piperazine ring, and de-swelled in basic solutions. The presence of PEGMA in the hydrogel enhanced the swelling and imparted water-responsive property, leading to disintegration at high concentration of 49.85%. The hydrogel was evaluated as an adsorbent for the removal of an anionic dye, Congo red (CR) from water. The dye uptake capacity of the hydrogel increased with increase in the initial dye concentration. Interestingly, the swelling ratio of the hydrogel decreased at high dye concentration due to the formation of additional physical crosslinks within the hydrogel matrix. The dye uptake capacity of the hydrogel decreased with increasing temperature due to the negative-temperature responsive property of the hydrogel. The time-dependent adsorption data was fitted with seven kinetic models. Pseudo second-order model best described the kinetics of adsorption process, and the adsorption of CR onto the hydrogel could be very well described with phase-boundary controlled models. The adsorption was a multistep process with surface adsorption followed by intraparticle diffusion.

In this work, stable and spherical silver nanoparticles (AgNPs) were synthesized in situ from silver salt (silver nitrate) using the aqueous extract of the okra plant (

In this work, stable and spherical silver nanoparticles (AgNPs) were synthesized in situ from silver salt (silver nitrate) using the aqueous extract of the okra plant (Abelmoschus esculentus) at room temperature and ambient pH conditions. The influences of different parts of the plant (such as the leaves, stems, and pods) on the chemical-reducing effectiveness of silver nitrate to silver nanoparticles were investigated. The aqueous extract of the leaves was found to be more effective in the chemical reduction of silver nanoparticles and in stabilizing them at the same time. The silver nanoparticles produced were stable and did not precipitate even after storage for 1 month. The extract of the stem was less effective in the reduction capacity followed by the extract of the pods. The results indicate that the different amounts of phytochemicals present in the leaves, stems, and pods of the okra plant are responsible for the chemical reduction and stabilizing effect. The silver nanoparticles were characterized by UV-Vis spectroscopy, Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The surface plasmon resonance (SPR) peak at 460 nm confirmed the formation of silver nanoparticles. The nanoparticles were spherical with an average size of 16 nm and polycrystalline with face-centered cubic (fcc) structures. The z-scan technique was used to study the nonlinear refraction and absorption coefficients of AgNPs at wavelengths of 488 and 514 nm under C.W. mode excitation. The nonlinear refraction index and nonlinear absorption coefficients were calculated in the theoretical equations in the experimental data. The antibacterial properties of the nanoparticles were evaluated against Gram-positive and Gram-negative bacteria.

The wildfire-like spread of COVID-19, caused by severe acute respiratory syndrome-associated coronavirus-2, has resulted in a pandemic that has put unprecedented stress on the world’s healthcare systems and caused varying severities of socio-economic damage. As there are no specific treatments to combat the virus, current approaches to overcome the crisis have mainly revolved around vaccination efforts, preventing human-to-human transmission through enforcement of lockdowns and repurposing of drugs. To efficiently facilitate the measures implemented by governments, rapid and accurate diagnosis of the disease is vital. Reverse-transcription polymerase chain reaction and computed tomography have been the standard procedures to diagnose and evaluate COVID-19. However, disadvantages, including the necessity of specialized equipment and trained personnel, the high financial cost of operation and the emergence of false negatives, have hindered their application in high-demand and resource-limited sites. Nanoparticle-based methods of diagnosis have been previously reported to provide precise results within short periods of time. Such methods have been studied in previous outbreaks of coronaviruses, including severe acute respiratory syndrome-associated coronavirus and middle east respiratory syndrome coronavirus. Given the need for rapid diagnostic techniques, this review discusses nanoparticle use in detecting the aforementioned coronaviruses and the recent severe acute respiratory syndrome-associated coronavirus-2 to highlight approaches that could potentially be used during the COVID-19 pandemic.

Biosurfactants (BSs) attract increasing attention as sustainable alternatives to petroleum-derived surfactants. This necessitates structural insight into how BSs interact with proteins encountered by current chemical surfactants. Thus, small-angle x-ray scattering (SAXS) has been used for studying the structures of complexes made of the proteins α-Lactalbumin (αLA) and myoglobin (Mb) with the biosurfactant rhamnolipid (RL). For comparison, complexes between αLA and the chemical surfactant sodium dodecyl sulfate (SDS) were also investigated. The SAXS data for pure RL micelles can be described by prolate core-shell structures with a core radius of 7.7 Å and a shell thickness of 12 Å, giving an aggregation number of 11. The small core radius is attributed to RL's complex hydrophobic tail. Data for the αLA-RL complex agree with a 12-molecule micelle with a single protein molecule in the shell. For Mb-RL, the analysis gives complexes of two connected micelles, each containing 10 RL and one protein in the shells. αLA-RL and Mb-RL form surfactant-saturated complexes above 5.6 and 4.7 mM RL, respectively, leaving the remaining RL in free micelles. The SAXS data for SDS agree with oblate-shaped micelles with a core of 20 Å, core eccentricity 0.7, and shell thickness of 5.45 Å, with an aggregation number of 74. The αLA-SDS complexes contain a prolate micelle with a core radius of 11-14 Å and a shell of 8-12 Å with up to 3 αLA per particle and up to 43 SDS per αLA, both considerably larger than for RL. Unlike the RL-protein complexes, the number of surfactant molecules in αLA-SDS complexes increases with surfactant concentration, and saturate at higher surfactant concentrations than αLA-RL complexes. The results highlight how RL and SDS follow similar overall rules of self-assembly and interactions with proteins, but that differences in the strength of protein-surfactant interactions affect the formed structures.

New stimuli-responsive cationic hydrogels based on N-acryloyl-N′-propyl piperazine (AcrNPP) were prepared using two types of chemical crosslinkers, viz., N,N-methylene bisacrylamide (Mba) and 1,4-butanediol diacrylate (Bda), respectively. The solubility parameter of the hydrogels was evaluated by equilibrium swelling experiment in a series of twelve solvents with well-distributed range of solubility parameters. The hydrogels exhibited maximum equilibrium swelling ratio in 1-butanol. The experimental swelling data were analyzed by two methods, (1) non-linear curve fitting and (2) least-square regression to determine the solubility parameter of the hydrogels. The solubility parameter determined by the two methods was in the range 11.45–11.85 (cal cm−3)1/2. The solubility parameter of the hydrogel containing the hydrophilic crosslinker (Mba) was higher than the hydrogel with a hydrophobic crosslinker (Bda), in all cases. This showed that the nature of chemical crosslinker influences the swelling and thus the solubility parameter of the hydrogels. The partial solubility parameter of the hydrogels related to the cohesive energy was evaluated by plotting the equilibrium swelling data against dispersion forces, polar forces, and hydrogen bonding. It was observed that both polar forces and hydrogen bonding play an important role in the swelling of these cationic hydrogels. The solubility parameter and the related forces were also estimated theoretically using group contribution methods and compared with the experimental results.

New polyampholyte linear polymers and hydrogels based on N -acryloyl- N ′-ethyl piperazine (AcrNEP) and maleic acid (MaA) were prepared by free-radical solution polymerization. The microstructure of copolymers was statistically estimated by the terminal copolymerization model. A maximum tendency (80%) of alternating sequence of monomers units occurred at about 85 mol % of AcrNEP in the reaction feed. The copolymers at definite monomer compositions (40 mol % of AcrNEP and 59.6 mol % of MaA) exhibited lower critical solution temperature (LCST) behavior in water. The LCST was dependent on monomer composition, pH of external solution, type and concentration of simple salts. The isoelectric points (IEP) of copolymers were found to be influenced by the overall composition of ionic monomer units. The influence of high maleic acid content (14 mol % and 59 mol %) and the type of chemical crosslinker on pH-responsive swelling behavior, water diffusion and dye sorption properties of the hydrogels were studied in detail. The gels exhibited interesting swelling behavior as function of pH (ionic strength = 0.01 M) due to a combination of factors such as pK a of the monomers, charge density, and type of crosslinker. The IEP of the gels were also determined from swelling experiments. The swelling ratio of the gels increased at the IEP with increase in ionic strength of the solution due to anti-polyelectrolyte effect. However below the IEP, the swelling ratio decreased considerably. Dynamic swelling properties of the amphoteric gels in water without added salt were measured. The swelling behavior was found to depend on the ionization state of the monomers, and the swelling followed non-Fickian (anomalous) mechanism. The swelling process of the hydrogels in water followed second-order kinetics. The amount of bound and unbound water in swollen gels was quantified using differential scanning calorimetry. Dye adsorption capacity of the new hydrogels was investigated using a Congo red as a model dye and was in the range 8.37–11.45 mg g −1 . This corresponds to an absorption efficiency of range 68–93%.

Stimuli-responsive cationic hydrogels based on N-acryloyl-N′-propyl piperazine (AcrNPP) crosslinked with N,N′-methylenebisacrylamide (Mba) and 1,4-butanedioldiacrylate (Bda) were prepared by UV light-initiated free-radical polymerization in bulk. The effect of external stimuli and type of crosslinker on the equilibrium swelling behavior and dynamic swelling was investigated in detail in buffer solution of various pH and temperatures. The equilibrium swelling capacity of the gels was large in swelling medium at pH 3.0 than at pH 10.0 due to ionization of polymer network under acidic conditions. With increase in temperature from 25 °C to 45 °C, the gels exhibited negative temperature-responsive (thermo-shrinking/thermophobic) behavior with negative activation energy for diffusion of water. The thermodynamic parameters such as Gibbs' free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) for the swelling of gels as function of temperature were negative indicating an exothermic swelling process. Water (media) transport mechanism and diffusion process in thin rectangular gels was studied. At pH 3.0, the diffusion process was non-Fickian (anomalous) while at pH 10.0 it was quasi-Fickian. The transport mechanism was partly influenced by the type of crosslinker in the gel. The dynamic swelling data was analyzed using early-time, late-time and Etters diffusion models. From the equilibrium swelling studies the average molecular weight between crosslinks (Mc), the crosslink density (ρc), and the mesh size (ξ) were determined. The Mc was large at pH 3.0 due to ionization of polymer and chain expansion. The experimental Mc was much larger than the theoretical Mc which implied that the gels were loosely crosslinked real networks. The mesh size of gels were between 447 and 786 A in the swollen (ionized) state (pH 3.0), and between 100 and 231 A in the collapsed (non-ionized) state (pH 10.0). The mesh size increased between three to four times during the pH-dependent swelling transition. The state of water in fully swollen hydrogels which influences many important biomaterial properties was determined by differential scanning calorimetry. The bound water content of gels increased linearly with increase in pH of the swelling medium while the unbound water decreased. These hydrogels have potential to be used as controlled drug delivery systems and sorbents for removal of pollutants from water.

Cationic polymers remain attractive tools for non-viral gene transfer. The effectiveness of these vectors rely on the ability to deliver plasmid DNA (pDNA) into the nucleus of cells. While we have previously demonstrated the potential of Lignin-PGEA-PEGMA as a non-viral gene delivery vector, alterations of cellular phenotype and cytotoxicity were observed post transfection. The present study aims to explore transfection conditions for high efficiency and low toxicity of the Lignin-PGEA-PEGMA based gene delivery system. Cellular toxicity was significantly reduced by using the centrifugation protocol, which enables rapid deposition of DNA complexes. Replacement of media post centrifugation resulted in minimal exposure of cells to excess polymers, which were toxic to cells. At an optimized DNA amount (500–750 ng) and molar ratios of nitrogen (N) in polymer to phosphate (P) in pDNA (N/P = 30–40), with the use of a novel transfection enhancer that facilitates endosomal escape and nuclear trafficking, the efficiency of gene delivery was increased significantly 24 h post transfection. The present study demonstrated an appropriately optimized protocol that enabled the utility of a novel cationic polymer blend with a mixture of fusogenic lipids and a histone deacetylate inhibitor in non-viral transfection, thereby providing an attractive alternative to costly commercial gene carriers.

Antioxidant is critical for the successful of nerve tissue regeneration, and biomaterials with antioxidant activity might be favorable for peripheral nerve repair. Lignin, a biopolymer from wood with excellent antioxidant properties, is still “unexplored” as biomaterials. To design an antioxidative bioscaffold for nerve regeneration, here we synthesized lignin-polycaprolactone (PCL) copolymers via solvent free ring-opening polymerization (ROP). Then such lignin-PCL copolymers were incorporated with PCL and engineered into nanofibrous scaffolds for supporting the growth of neuron and Schwann cell. Our results showed that the addition of lignin-PCL enhanced the mechanical properties of PCL nanofibers and endowed them with good antioxidant properties (up to 98.3 ± 1.9% free radical inhibition within 4 h). Cell proliferation assay showed that PCL/lignin-PCL nanofibers increased cell viability compared to PCL fibers, especially after an oxidative challenge. Moreover, Schwann cells and dorsal root ganglion (DRG) neurons cultured on the nanofibers to assess their potential for nerve regeneration. These results suggested that nanofibers with lignin copolymers promoted cell proliferation of both BMSCs and Schwann cells, enhanced myelin basic protein expressions of Schwann cells and stimulated neurite outgrowth of DRG neurons. In all, these sustainable, intrinsically antioxidant nanofibers may be a potential candidate for nerve TE applications.

Stimuli-responsive, smart, intelligent, or environmentally sensitive polymers respond to changes in external stimuli such as pH, temperature, ionic strength, surfactants, pressure, light, biomolecules, and magnetic field. These materials are developed in various network architectures such as block copolymers, crosslinked hydrogels, nanogels, inter-penetrating networks, and dendrimers. Stimuli-responsive cationic polymers and hydrogels are an interesting class of “smart” materials that respond reversibly to changes in external pH. These materials have the ability to swell extensively in solutions of acidic pH and de-swell or shrink in solutions of alkaline pH. This reversible swelling-shrinking property brought about by changes in external pH conditions makes these materials useful in a wide range of applications such as drug delivery systems and chemical sensors. This article focuses mainly on the properties of these interesting materials and their applications in drug delivery systems.

New temperature-responsive hydrogels containing various composition of N-acryloyl morpholine (AM) and N-isopropyl acrylamide (NIPAM) were prepared by free-radical solution polymerization using poly(ethyleneglycol) diacrylate (PEGDA) as the chemical crosslinker. The gels were responsive to changes in external temperature, and exhibited the volume phase transition phenomenon. The gels swelled extensively in water at 23°C, with water-uptake of more than 90% at swelling equilibrium. The influence of molecular heterogeneity of the gels in terms of co-monomer and crosslinker composition on the swelling capacity and equilibrium water uptake was evaluated. The dye adsorption capacity of the gels at room temperature was studied using Congo red as a model dye. The gels displayed significant adsorption capacity of the dye, and the adsorption capacity was found to be dependent on the hydrophilic character of the gel. The characteristic adsorption parameters were determined using the Langmuir isotherm model. The value...

New multi-stimuli responsive cationic copolymers based on N-acryloyl-N′-ethyl piperazine (AcrNEP) and N-isopropylacrylamide (NIPAM) were prepared by thermal free-radical solution polymerization in dioxane at 75 °C. The chemical composition of the copolymers was determined by 1H NMR spectroscopy and was found that the copolymers were slightly rich in NIPAM content than that of AcrNEP. The reactivity of the two monomers for the copolymerization reaction was evaluated by the extended Kelen-Tudos method. The distribution of monomer sequence in the copolymer chain was estimated using the terminal copolymerization model. The maximum tendency to alternation (∼ 70%) was at 60 mol % of AcrNEP in the monomer feed. The copolymers were readily soluble in water at room temperature at all compositions and exhibited well-defined lower critical solution temperature (LCST) phenomenon. The influence of various stimuli such as pH, temperature, simple inorganic salts, and surfactants on the LCST of the copolymers was studied in detail. Simple inorganic salts such as sodium chloride, sodium bromide, and sodium sulfate showed a salting-out effect while sodium iodide showed a salting-in effect. The salting-out coefficient of the salts were calculated using the Sestchenow method, and the salting trend followed the order SO42− > Cl− > Br− > I−. The divalent salt was more effective in lowering the LCST than the monovalent salts. The cationic surfactant hexadecyl trimethylammonium bromide at concentrations above the critical micelle concentration caused a gradual increase in the LCST of the copolymer solutions. The intrinsic viscosity and light scattering behavior of the copolymers in water and in sodium chloride solutions were studied in detail. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1175–1183

Hydrogels composed of N-isopropyl acrylamide and sodium acrylate were prepared using a new stiff crosslinker 1,4-diacryloyl piperazine by a room-temperature free-radical solution polymerization. The gels swelled extensively in water and the swelling increased with increase in sodium acrylate content. Compared to similar gels with N,N’-methylene bisacrylamide as crosslinker the swelling ratio was lower by 25%. Silver nanoparticles were prepared in the hydrogel matrix by in-situ chemical reduction of silver nitrate with sodium borohydride. The new crosslinker being hydrophobic with less structural flexibility controlled the diffusion of silver and borohydride ions into the gel matrix. Silver nanoparticles were formed only on the periphery of the gel as diffusion into the central matrix was hindered by the nonflexible crosslinker. The gels were responsive to temperature changes and the difference in equilibrium water content from 23 to 55°C was 4.5-fold due to strong hydrophobic interactions. The temperature...

New cationic linear copolymers of N-vinyl caprolactam (VCL) and N-acryloyl-N′-ethyl piperazine (AcrNEP) were synthesized by thermal free-radical solution polymerization in dioxane at 75 °C. The chemical composition of the copolymers was determined by 1H NMR spectroscopy. The copolymers were water-soluble at all composition and exhibited lower critical solution temperature (LCST) behavior. The LCST was greatly influenced by the AcrNEP content, changes in pH, temperature, salt and surfactant concentration of the external medium. The copolymers were rich in AcrNEP content due to its higher reactivity over VCL. The reactivity of AcrNEP and VCL were determined by the extended Kelen–Tüdös method to be r1AcrNEP = 0.41 and r2VCL = 0.13. The distribution of monomer sequence in the polymer chain was estimated using the terminal copolymerization model and the maximum tendency to alternation (70%) was at 45 mol % of AcrNEP in the feed. The effect of polymer concentration in the range 0.02 to 20 wt % on the LCST behavior showed a rather exponential decrease with the effect being more significant in the dilute regime. Simple inorganic salts such as sodium chloride and sodium bromide showed a salting-out effect while sodium iodide showed a salting-in effect of the copolymers in water. The salting-out coefficient of sodium chloride and sodium bromide evaluated by the Sestchenow equation was 1.37 and 1.12 L mol–1, respectively. The salting trend followed the order Cl– > Br– > I–. The intrinsic viscosity behavior and second-virial coefficient of the copolymers in water and in sodium chloride solution was studied in detail. Cross-linked cationic hydrogels of VCL and AcrNEP with a flexible (N,N′-methylenebisacrylamide) and stiff (1,4-diacryloyl piperazine) chemical cross-linker were prepared. The gels were responsive to pH and temperature changes of external medium. The influence of cross-linker type on the properties of the gels in terms of stimulus response, water transport mechanism, diffusion, and adsorption of an anionic dye (Congo red) were studied in detail.

New functional linear copolymers and crosslinked gels based on a disubstituted heterocyclic acrylamide, i.e., N-acryloyl-N′-phenyl piperazine (AcrNPhP) with acrylic acid (AA) and hydroxyethyl methacrylate (HEMA) were prepared by thermal free-radical polymerization. The composition of the linear copolymers was analyzed by infra-red spectral analysis and elemental analysis methods. The reactivity parameters of the monomers were determined by the Finemann-Ross and Kelen–Tudos linearization methods. Using the values obtained from the Kelen–Tudos linearization methods, the reactivity or resonance stabilization (Q) and polarity (e) of AcrNPhP with AA and HEMA were calculated (AcrNPhP–AA system Q = 1.9, e = −0.6, and AcrNPhP–HEMA system Q = 2.5, e = −1.2). Crosslinked copolymer hydrogels of AcrNPhP with AA and HEMA were prepared by bulk and solution polymerization methods. The method of preparation, the type of crosslinker and monomers showed a profound impact on the pH responsive swelling of the gels. The hydrogels were highly responsive to changes in external pH. The gels composed of AcrNPhP and AA swelled more than 1,200 % above the pK a of acrylic acid. Interestingly, no significant swelling (about 1 %) was observed in solution of low pH (acidic) despite the presence of an ionizable tertiary amine function in the polymer network. This is attributed to the presence of a bulky phenyl group at the tertiary amine function of AcrNPhP which sterically hinders the protonation and thereby the final swelling of the gel. The gels composed of AcrNPhP and HEMA did not display a significant pH responsive behavior due to the same effect. The AcrNPhP–HEMA gel-containing 70 % AcrNPhP swelled to only 50 % despite the presence of a large fraction of the ionizable unit.

Poly(N-acryloyl-N0-ethyl piperazine-co-N-isopropyla- crylamide) hydrogels were prepared by thermal free-radical copolymerization of N-acryloyl-N 0 -ethyl piperazine (AcrNEP) and N-isopropylacrylamide (NIPAM) in solution using N, N 0 - methylene bisacrylamide as the crosslinking agent. The gels were responsive to changes in external stimuli such as pH and temperature. The pH and temperature responsive character of the gels was greatly dependent on the monomer content, namely AcrNEP and NIPAM, respectively. The gels swelled in acidic (pH 2) and de-swelled in basic (pH 10) solutions with a response time of 60 min. With increase in temperature from 23 to 80 � C the swelling of the gels decreased continuously and this effect was different in acidic and basic solutions. The tem- perature dependence of equilibrium water content of the gels was evaluated by the Gibbs-Helmholtz equation. Detailed anal- ysis of the swelling properties of these new gels in relation to molecular heterogeneity in acidic (pH 2) and basic (pH 10) solu- tions were performed. Water transport property of the gels was studied gravimetrically. In acidic solution, the diffusion process was non-Fickian (anomalous) while in basic solution, the diffusion was quasi-Fickian. The effect was more evident in solution of pH 2 than in pH 10. Various structural parameters of the gels such as number-average molar mass between crosslink (Mc), the crosslink density (qc), and the mesh size (n) were evaluated. The mesh sizes of the hydrogels were between 64 and 783 Ain the swollen state in acidic solution and 20 and 195 Ain the collapsed state in basic solution. The mesh size increased between three to four times during the pH-depend- ent swelling process. The amount of unbound water (free water) and bound water of the gels was also evaluated using differential scanning calorimetry. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 000: 000-000, 2012

New hydrogels based on N-acryloyl-N′-ethylpiperazine (AcrNEP) and N,N-methylene bisacrylamide (MBA) were prepared by thermal initiated solution polymerization. The hydrogels swelled extensively in buffer solutions of low pH due to protonation of the amine functions of the monomers, while the swelling was less significant in buffer solutions of high pH. The increased swelling of the gel in low pH is due to the development and interaction of fixed charges within the gel network. As a result of the electrostatic repulsion between the charges the elastic constraint of the gel is modified which leads to pronounced swelling and hence to high water uptake. Water transport in the hydrogel both in buffer solutions of pH 2.6 and pH 8.4 was non-Fickian due to polymer relaxation (anomalous process). The gels demonstrated good uptake of divalent metal ions such as Ni2+, Co2+, and Zn2+, with high selectivity for Ni2+ ions due to the formation of a more stable ligand-metal complex. The metal uptake capacity increased wi...

The formation and growth of titania (anatase) nanoparticles in benzyl alcohol from TiCl4 was studied in situ at 85 °C via powder X-ray diffraction (PXRD), small-angle X-ray scattering (SAXS), and turbidimetry. The results provide new information on the kinetics of this process and allow for better control of particle size, shape, and aggregation. Rietveld refinement of ex situ PXRD data shows that the final crystals are anisotropic in shape and elongated along the crystallographic c-axis. In situ SAXS and PXRD show that the crystals form suddenly after a lag period. The crystals are initially isotropic in shape and the growth is isotropic; thereafter, the growth proceeds predominantly along the crystallographic c-axis to form anisotropic crystals, in agreement with the ex situ PXRD results. The relative lattice strain, which is determined as the lattice deformation relative to the lattice constants found late in the growth process, is positive along the c-axis and negative, but smaller, along the a-axis. ...

A clear and stable nonionic model microemulsion consisting of pentaoxyethylene glycol dodecyl ether (C(12)E(5)), water, and 1-chlorotetradecane (CLTD) was prepared. This system was subjected to a systematic temperature quench (perturbation out of equilibrium) in steps of 1.0 degrees C from 20.4 to 15.3 degrees C in the unstable region of its phase diagram. The change in turbidity (for droplet volume fractions of 0.02 and 0.08) and hydrodynamic radius (R(h)) (for a droplet volume fraction of 0.02) of the system on its way to its new equilibrium was measured at each quench temperature. For small systematic temperature quenches just below the emulsification failure boundary (EFB) the turbidity decreases and remains constant indicating quick changes in the microstructures. Further lowering of temperature brings the system to the unstable region where the turbidity and light scattering increase sharply as function of time because of expulsion of excess oil from the microemulsion droplets. The newly formed oil-rich droplets grow in size as a function of time. These observations indicate the existence of a narrow but observable metastable region en route to the new equilibrium where both microemulsion droplets and larger oil-rich droplets coexist. The region in which microemulsion droplets are metastable is very narrow and is concentration-dependent. The presence of a metastable region is as for other similar systems attributed to the presence of a free energy barrier for the formation of the larger oil-rich droplets associated with curvature free energy of the surfactant film. The turbidity-time curves were converted to the radius-time curves using a model assuming monodisperse spherical droplets. The obtained results are in good agreement with the results for the hydrodynamic radius. The observed average radius from both type of measurements decreases in the metastable region. By performing calculation of the influence of eccentricity and size polydispersity on the observed radius, we have shown that the distribution of the microemulsion droplets becomes more homogeneous in the metastable region.

Copolymers of N-acryloyl-N′-methylpiperazine (AcrNMP) and 2-hydroxyethyl methacrylate (HEMA) were synthesized by free radical solution polymerization in dioxane at 70 ± 1 °C, using 2,2′-azobisisobutyronitrile (AIBN) as initiator. The copolymer compositions were analyzed by the methods of FTIR spectroscopy and elemental analysis. Both the method of analysis yielded results that agreed reasonably well. The monomer reactivity ratios of the copolymerization were determined by the linearization methods of Finemann–Ross (FR) and Kelen–Tudos (KT). The reactivity parameter results derived using FTIR analysis showed that the copolymerization yielded mainly alternating structure with reactivity ratios, r1(AcrNMP) = 0.263 ± 0.011 and r2(HEMA) = 0.615 ± 0.097 by F–R method and r1 = 0.227 ± 0.074 and r2 = 0.53 ± 0.15 by KT method. Microstructure data calculated by the method of Igarashi also supports the alternating structure (tendency) of the copolymer. Crosslinked polymer gels of this system exhibited remarkably high swelling of more than 500% in water at ambient temperature.

The phase behavior and phase separation kinetics of a model ternary nonionic microemulsion system composed of pentaethylene glycol dodecyl ether (C12E5), water, and 1-chlorotetradecane were studied. With increasing temperature, the microemulsion exhibits the following rich phase behavior: oil-in-water phase (L1+O), droplet microemulsion phase (L1), lamellar liquid crystalline phase (Lproportional), and sponge-like (liquid) phase (L3). The microemulsion with a fixed surfactant-to-oil volume fraction ratio (Phis/Phio) of 0.81 and droplet volume fraction of 0.087 was perturbed from equilibrium by a temperature quench from the L1 region (24 degrees C) to an unstable region L1+O (13 degrees C), where the excess oil phase is in equilibrium with the microemulsion droplets. The process of phase separation in the unstable region was followed by time-resolved small-angle X-ray scattering (TR-SAXS) and time-resolved turbidity methods. Due to the large range of scattering vector (q=0.004-0.22 A(-1)) that is possible to access with the TR-SAXS method, the growth of the oil droplets and shrinking of the microemulsion droplets as a result of phase separation could be studied simultaneously. By using an advanced polydisperse ellipsoidal hard-sphere model, the experimental curves have been quantitatively analyzed. The microemulsion droplets were modeled as polydisperse core-shell ellipsoidal particles, using molecular constraints, and the oil droplets are modeled as polydisperse spheres. The radius of gyration (Rg) of the growing oil droplets, volume fraction of oil in the microemulsion droplets, and polydispersity were obtained from the fit parameters. The volume equivalent radius at the neutral plane between the surfactant head and tail of the microemulsion droplet decreased from 76 to 51 A, while the radius of oil drop increased to 217 A within the 160 min of the experiment. After about 48 min from the temperature quench, the system reaches a steady state and continues to coarsen at a constant fraction of the oil of 0.51 in the oil phase by Ostwald ripening with the power law dependence of Roil proportional, variant t1/3. The size of the oil droplets determined by the time-resolved turbidity method is in good agreement with that of the TR-SAXS, highlighting the usefulness of the method in the size determination of oil-in-water microemulsions on an absolute scale.

Monoquaternary cationic polymerizable surfactants of type N-acryloyl-N'-methyl-N-alkyl piperazinium bromide based on piperazine heterocycle was synthesized by reacting N-acryloyl-N'methyl piperazine with the corresponding n-alkyl bromide (decyl, dodecyl, tetradecyl, and hexadecyl) in anhydrous acetone at room temperature. The resulting surfactants were deliquescent to display any sharp melting points. The surface activity was studied by surface tension measurements. Due to the complex head group geometry of these surfactants, the critical micelle concentration value was high in comparison to the analogous alkyltrimethyl ammonium bromides of similar alkyl chain length. The surfactants were polymerized by micellar (in water) and isotropic (in benzene) conditions and the resulting polymers were characterized by solubility and viscosity studies. The polymers prepared in water showed higher viscosity than the ones prepared in benzene as a result of micellar aggregation in water. The reduced viscosity of the polymers in polar solvents such as methanol and dimethyl formamide (DMF) showed polyelectrolyte-like behavior, whereas nonelectrolyte behavior was observed in chloroform. pH-responsive hydrogels were prepared by polymerizing the surfactants in the bicontinuous phase of a microemulsion. The resulting polymers did not exhibit any definite micro/nanostructure due to cross-polymerization of the hydrophilic oil in the bicontinuous network structure. The gels were highly responsive to changes in pH of the medium and showed high-swelling degree in acidic media owing to the protonation of the tertiary nitrogen of the piperazine ring.

New non-ionic microemulsions consisting of pentaethyleneglycol dodecyl ether, water, and 1-chloroalkanes were prepared, and their phase behavior was studied. A homologous series of five different 1-chloroalkanes from 1-chlorooctane to 1-chlorohexadecane was studied. The phase behavior of the microemulsions was determined by vertical sections through the Gibbs' phase prism ("fish" plots), from which valuable information such as the microemulsion balance temperature (T(0)), efficiency of the surfactant (phi*), temperature extension of the three-body phase (DeltaT), mean temperature (T(m)), and the monomeric solubility in oil (phi(mon,oil)) was obtained. The chlorinated alkanes in the microemulsions shift the balance temperature to about 14 degrees C lower compared with their n-alkane counterparts. This indicates the polar nature of the chlorinated oils and their ability to penetrate the surfactant film. The chlorinated alkanes thus behave as short n-alkane molecules and lower the spontaneous curvature of the microemulsion droplets. The efficiency of the surfactant and the monomeric solubility in oil systematically depend on the alkyl chain length of the oil, with the efficiency and solubility decreasing with increasing alkyl chain length of 1-chloroalkane. The size and shape of the microemulsion droplets in the microemulsion phase were studied by small-angle X-ray scattering (SAXS). For a surfactant-to-oil volume fraction ratio of 0.80, the droplets can be described by ellipsoidal shapes, and the size of the droplets increased with increasing alkyl chain length.

pH responsive copolymer nanogel particles of N‐acryloyl‐N′‐methyl piperazine (AcrNMP) and methyl methacrylate (MMA) were prepared by a suitable oil‐in‐water type microemulsion polymerization. Effect of microemulsion polymerization conditions such as water content, surfactant‐to‐monomer ratio, amount of monomer, and crosslinker content were studied. The nanogel particles showed spherical morphology with narrow size distribution. The nanogels swelled excessively in acidic solutions reaching a diameter of 750 nm and de‐swelled to 350 nm in basic solutions. This pH response to swelling is due to the protonation of N′‐methyl piperazine nitrogen that leads to electrostatic interactions within the nanogel.

Nanoemulsions are an interesting part of multiphase colloidal dispersions with many interesting properties and applications. Nanoemulsions consist of nanoscale droplets formed mainly by shear-induced rupturing. The interesting properties, formation, stability, and general characteristics of nanoemulsions are described in this chapter. The nanoemulsions are popular due to their stability, optical transparency, diffusion characteristics and are widely used in the food industry for flavor encapsulation, food preservation, food safety, and to maintain food quality. Due to their encapsulation properties these systems are also used in pharmaceutical sciences for targeted drug delivery applications.

The phase behavior and structure of a four-component microemulsion system forming droplets with an oil core surrounded by the non-ionic C 12 E 5 surfactant in water and "decorated" by long PEO chains using the block copolymer/ surfactant Brij 700 has been studied. The surfactant-to-oil volume ratio, the coverage density of the droplets with decorating molecules, and the temperature were varied. For a surfactant-to-oil volume ratio of 2, the solutions form isotropic and clear solutions at room temperature, and the addition of Brij molecules stabilize the micelles: the transition to an opaque phase is shifted to higher temperatures as the surface coverage increases. At a surfactant-to-oil ratio of 1, the isotropic microemulsion phase is confined to a very narrow range of temperature, which location is shifted to increasing temperature, as the amount of Brij at the surface of the droplet is increased. For large surface coverages, the lower emulsification boundary varies roughly linearly with the surface coverage. The structure of the droplet phase was investigated by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). For a surfactant-to-oil ratio of 2, the SANS data revealed a transition from rodlike to spherical particles when Brij molecules are added to the system, which induces a larger curvature of the surfactant film. For a surfactant-to-oil ratio of 1, the droplets are nearly spherical at all surface coverages. The intermicellar interactions effects become increasingly more pronounced as Brij is added, due to the introduction of the highly swollen corona. A quantitative analysis of some of the SAXS data was done using an advanced model based on Monte Carlo simulations. It demonstrates the strong chain-chain interactions within the corona and confirms the increased interparticle interactions, as the coverage density is increased.

To investigate the structural development of the colloid phases generated during lipolysis of a lipid-based formulation in an in vitro lipolysis model, which simulates digestion in the small intestine.Small-Angle X-Ray scattering (SAXS) coupled with the in vitro lipolysis model which accurately reproduces the solubilizing environment in the gastrointestinal tract and simulates gastrointestinal lipid digestion through the use of bile and pancreatic extracts. The combined method was used to follow the intermediate digestion products of a self nano emulsified drug delivery system (SNEDDS) under fasted conditions. SNEDDS is developed to facilitate the uptake of poorly soluble drugs.The data revealed that a lamellar phase forms immediately after initiation of lipolysis, whereas a hexagonal phase is formed after 60 min. The change of the relative amounts of these phases clearly demonstrates that lipolysis is a dynamic process. The formation of these phases is driven by the lipase which continuously hydrolyzes triglycerides from the oil-cores of the nanoemulsion droplets into mono- and diglycerides and fatty acids. We propose that this change of the over-all composition of the intestinal fluid with increased fraction of hydrolyzed nanoemulsion induces a change in the composition and effective critical packing parameter of the amphiphilic molecules, which determines the phase behavior of the system. Control experiments (only the digestion medium) or the surfactant (Cremophor RH 40) revealed the formation of a lamellar phase demonstrating that the hexagonal phase is due to the hydrolysis of the SNEDDS formulation.The current results demonstrate that SAXS measurements combined with the in vitro dynamic lipolysis model may be used to elucidate the processes encountered during the digestion of lipid-based formulations of poorly soluble drugs for oral drug delivery. Thus the combined methods may act as an efficient screening tool.

Linear homopolymers of N-acryloyl-N′-alkyl piperazine (N′-alkyl: methyl, ethyl, or propyl) and their corresponding crosslinked hydrogels were prepared. The polymers showed good responses to changes in the pH of the medium due to the presence of tertiary amine functions that could be protonated at a low pH. The nature of the N′-alkyl group attached to the piperazine amino nitrogen greatly affected the pKa of the amino group. This in turn influenced the solution behavior of the polymers and was studied with light scattering, potentiometry, and viscosity measurements. The basicity of the polymers increased with an increase in the chain length of the N′-alkyl substituent. The intrinsic viscosity of the polymers in a good polar organic solvent such as dimethylformamide decreased slightly with increasing temperature because of decreased thermodynamic affinity (interaction) at high temperatures. The viscosity behavior of the polymers in sodium chloride solutions was similar to that of classical polyelectrolytes. The swelling property of the hydrogels was studied with water sorption measurements, and the swelling was by anomalous (non-Fickian) transport. The diffusion coefficient of the gels in solutions of pH 2.6 increased with increasing N′-alkyl chain length, whereas at neutral pH, the effect was reversed. This behavior was attributed to the increase in both the basicity and hydrophobicity of the gels with an increase in the chain length of the N′-alkyl groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

The delivery of genetic materials into cells to elicit cellular responses has been extensively studied by biomaterials scientists globally. Many materials such as lipids, peptides, viruses, synthetically modified cationic polymers and certain inorganic nanomaterials could be used to complex the negatively charged plasmids and deliver the formed package into cells. The recent literature on the delivery of genetic materials utilising inorganic nanoparticles is carefully examined in this review. We have picked out the most relevant references and concisely summarised the findings with illustrated examples. We further propose alternative approaches and suggest future pathways towards the practical use of multifunctional nanocarriers.

Hydrogel nanocomposites containing silver nanoparticles of size 15–21 nm were prepared by diffusion and in-situ chemical reduction in chemically crosslinked polymers based on N-acryloyl-N′-ethyl piperazine (AcrNEP) and N-isopropylacrylamide (NIPAM). The polymer chains of the hydrogel network offered control and stabilization of silver nanoparticles without the need for additional stabilizers. The presence of silver nanoparticles and their size was quantified by UV-Vis absorption spectroscopy and scanning electron microscopy. The nanocomposite hydrogels were responsive to pH and temperature changes of the external environment. The equilibrium weight swelling ratio of the hydrogel nanocomposite was lower in comparison with the precursor hydrogel. Silver nanoparticles present in the nanocomposite offered additional physical crosslinking which influenced media diffusion and penetration velocity. The release of silver nanoparticles from the hydrogel matrix in response to external pH changes was studied. The rate of release of silver nanoparticles was higher in a solution of pH 2.5 due to maximum swelling caused by ionization of the gel network. No significant release of nanoparticles was observed in a solution of pH 7.

‘Stimuli’ responsive copolymers of N-acryloyl-N′-ethyl piperazine (AcrNEP) and methyl methacrylate (MMA) were synthesized by free radical solution polymerization. The copolymers were analyzed as thin films by FTIR spectroscopy. The monomer reactivity ratios were determined by linearization methods of Fineman–Ross (F–R) and Kelen–Tudos (K–T) giving the results r1 (AcrNEP)=0.58 and r2 (MMA)=0.91 by the F–R method and r1=0.72 and r2=1.08 by the K–T method. The latter r values in turn yielded Q=0.59 and e=−0.12 for AcrNEP. Crosslinked copolymer hydrogels of AcrNEP and MMA with various compositions were prepared in bulk and solution by photo-initiated free-radical polymerization. The gels were dual responsive to pH and temperature. The response to pH was reversible with a response time of 100 min with good reversibility and with no loss in swelling capacity. Water sorption of the gels was investigated gravimetrically and the collective diffusion coefficients were determined at 10, 25, and 50 °C. The water sorption of the gels in water was Fickian. The temperature dependence of the equilibrium water content was studied by the Gibbs–Helmholtz equation. The enthalpy of mixing decreased with an increase in the hydrophilic content (AcrNEP) of the gel. Other parameters such as type and amount of crosslinker, preparative conditions, nature of buffers, and salts were found to influence the swelling behavior.

An oil-in-water microemulsion of the system C12E5/water/ n-decane with a fixed surfactant-to-oil volume fraction ratio φs/φo of 0.85 is studied. This clear microemulsion is temperature-quenched from a clear one-phase region (26 °C) with spherical microemulsion droplets to an unstable region (13 °C) where the excess oil phase is in equilibrium with the microemulsion droplets. Using a high-resolution version of a laboratory small-angle X-ray scattering (SAXS) instrument, the evolution of the excess oil and its growth as a function of time is studied. Unlike coarsening in alloys and polymer blends, a maximum in the intensity at a finite scattering vector is not observed. This clearly indicates that the droplet of the excess oil is formed homogeneously and that there is no depletion zone around the formed droplets. The scattering curves are quantitatively analysed as a function of time. The microemulsion droplets are modeled as polydisperse core-shell ellipsoidal particles, using molecular constraints and the oil droplets are modeled as polydisperse spheres. The average radius of the oil droplets increases with a scaling exponent in agreement with that of coarsening of precipitates in alloys and phase separations in polymer blends, suggesting some degree of universality of coarsening processes.

By using a powder method, a new method for producing semiconductor/polymer nanocomposites, lead sulfide (PbS) nanoparticles were prepared and dispersed in either poly(methylmethacrylate-co-methacrylic acid) or poly(styrene-co-styrenesulfonic acid). The size of the nanoclusters was less than 2 nm, and the size distribution was rather sharp, determined by UV–vis absorption spectroscopy. The absorption spectra of the PbS-containing sheets showed a blue shift and the absorption edges were steep, reflecting the formation of nano-sized PbS clusters. The spectra also exhibited an absorption maximum, which is an indication of a narrow particle size distribution. The glass transition temperature (Tg) of the PbS-containing nanocomposites was higher than that of the corresponding ionomer. The effect of heat treatment on the aggregation of PbS is also discussed. The dissolution of powder samples, followed by neutralization of acidic groups, led to reduction of particle sizes, suggesting the usefulness of ionic groups for stabilizing PbS nanoclusters.

A piperazine-based cationic surfactant, N , N ′-dimethyl- N -acryloyloxyundecyl piperazinium bromide (DAOUPB) was synthesised by a two-step procedure. The monomer was polymerised in two new microemulsion systems: (i) DAOUPB/water/methyl methacrylate (MMA):hydroxyethylmethacrylate (HEMA) and (ii) DAOUPB/water/acrylonitrile with ethyleneglycol dimethacrylate (EGDMA) as the crosslinking agent. Transparent solid polymeric materials were obtained by photo-initiated polymerisation of some of these microemulsion compositions. Most of the bicontinuous microemulsions investigated gelled within 10 min resulting in transparent solid polymers. The electron micrographs of the polymers obtained from microemulsion compositions containing MMA:HEMA did not show any micropores, while those obtained using acrylonitrile revealed the existence of open-cell type micropores and also of the bicontinuous nature of the system. The width of the bicontinuous structure (micropores) was about 33 nm in the dry state, with long and winding channels of random distribution. The swelling of the gels was highly sensitive to pH.

Neodymium(III) oxide nanocrystals prepared by an inverse microemulsion technique have been dispersed in sol-gel titania/(γ-glycidoxypropyl)trimethoxysilane composite thin films at low temperature. Transmission electron microscopy and x-ray diffraction were used to characterize the phosphor nanoparticles and show that the neodymium(III) oxide nanoparticles have a nanocrystal structure and the size of the nanoparticles is in the range from 5 to 60 nm. An intense up-conversion emission in violet (399 nm) color from neodymium(III) oxide nanocrystals upon excitation with a yellow light (577 nm) has been observed. Two ultraviolet emissions at 347 and 372 nm and a blue emission at 466 nm have also been observed, and those are assigned to electronic transitions appropriately. A relatively strong room-temperature photoluminescence emission at 1064 nm corresponding to the 4F3/2 → 4I11/12 transition of neodymium ion has been measured as a function of the heat treatment temperature. In addition to this emission, two other emissions at 890 and 1336 nm have also been observed. Especially, a clear shoulder peak at 1145 nm, which could probably be resulting from the host matrix, was observed in all measured samples, and this shoulder peak reached a maximum intensity after a heat treatment at 300 °C.

This paper presents an up-conversion emission in violet (404 nm) color from neodymium oxide and neodymium oxalate nanoparticles upon excitation with a yellow light (580 nm). Powder phosphors of neodymium oxide and neodymium oxalate nanoparticles were synthesized by the microemulsion technique. In addition to this violet emission, two UV emissions at 342 and 370 nm, and a weak blue emission at 450 nm have been observed and these are assigned to electronic transitions appropriately. The lifetimes of the violet color emission transition at 404 nm have been obtained; the mechanism of the up-conversion emission has heen explained. The oxide-based phosphor has shown strong up-conversion emission compared to the oxalate-based phosphor. The transmission electron microscopy (TEM) measurement shows that the oxide phosphor is in nanocrystal structure.

This paper reports the preparation and characterization of erbium oxalate and erbium oxide nanoparticles. The erbium oxalate and erbium oxide phosphor materials were synthesized through the microemulsion technique. Transmission electron microscopy (TEM) was used to characterize the phosphor materials and reveal a nanocrystal structure for the studied phosphors. A strong green up-conversion emission at 543 nm ( 4 S 3/2 → 4 I 15/2 ) and another weak emission at 528 nm ( 2 H 11/2 → 4 I 15/2 ) have been measured for the studied phosphors upon excitation at 993 nm ( 4 I 11/2 → 4 I 15/2 ). The up-conversion emission mechanism has been explained by means of an energy level diagram. The lifetimes of these emissions have been measured. The green up-conversion emission equally strong in both the phosphors and for these phosphors, color coordinates ( X , Y ) have been obtained in order to assess their color emitting efficiency.

New crosslinked copolymer hydrogels of N -acryloyl- N ′-methyl piperazine and methyl methacrylate in various compositions were prepared in bulk and solution by photo-initiated free-radical polymerization. The gels exhibited both pH and temperature sensitivities. The response to pH was reversible with a response time of 150 min. The water sorption of the gels was investigated gravimetrically and the collective diffusion coefficients were determined according to the Fickian kinetics at 10°C, 25°C, and 50°C. The apparent activation energy was independent of the composition of the gel networks with a value of 6.26 kJ mol −1 corresponding to a typical diffusion process. The temperature dependence of the equilibrium water content was analyzed by the Gibbs–Helmholtz equation. The enthalpy of mixing decreased with an increase in the hydrophilic content of the gel.

This paper reports the preparation and fluorescence characteristics of erbium (III) oxide nanocrystals. The erbium oxide phosphors were synthesized through a microemulsion technique. Transmission electron microscopy and X-ray diffraction were used to characterize the phosphor nanoparticles and reveals a nanocrystal structure and the size in the range from 5 to 30 nm in diameter. A room-temperature photoluminescence was observed at 1.54 μm with a full width at half-maximum (FWHM) of 22 nm due to intra-atomic transitions ( 4 I 13/2 → 4 I 15/2 ) levels in the erbium (III) ions. It was also observed that the shape and the FWHM of the photoluminescence signals from the composite film prepared by embedding the nanocrystals into titania/organically modified silane composite matrix are quite similar to those from the nanocrystal, but its peak position shifted from 1.540 μm to 1.531 μm.

Hydrogels based on N-acryloyl-N'-methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non-Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 x 10 -7 and 5.00 x 10 -7 cm -2 s -1 , respectively. These gels demonstrated good metal-uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal-loaded gels could be stripped easily with 1M H 2 SO 4 without any loss in their uptake capacity.

Erbium (III) oxalate nanoparticles dispersed titania/y-Glycidoxypropyltrimeth-oxysilane composite materials for photonic applications were prepared by a chemical approach combining the microemulsion technique and the sol-gel method at low temperature. Transmission electron microscopy observation shows that the size of the erbium (III) oxalate nanoparticles is in the range from 10 to 40 nm. A relatively strong room-temperature green up-conversion emission at 543 nm (4S3/2→4I15/2) has been measured for the composite thin films with different erbium oxalate content and heat treatment temperature upon excitation at 993 nm. The lifetime of the visible up-conversion emission has been measured. UV-visible transmission spectroscopy results showed that a relatively high transparency (in the visible range) composite thin film could be obtained at a suitably low heat treatment temperature.

Water-soluble copolymers of N-acryloyl-N′-alkylpiperazine (alkyl: methyl, ethyl) with methyl methacrylate were synthesized and the lower critical solution temperatures (LCSTs) of the copolymers which depend on the compositions and pH of the aqueous solutions are described. The effects of cationic surfactants and simple inorganic salts on the LCSTs are also reported. The influences of pH and temperature on the swelling of the ionizable and thermosensitive hydrogels are studied.

A new water-soluble stimuli-responsive poly(N-acryloyl-N‘-propylpiperazine) (PAcrNPP) was synthesized and characterized. The polymer exhibited a lower critical solution temperature (LCST) in water ...

Copolymers of N -acryloyl- N′ -methylpiperazine (AcrNMP) and methyl methacrylate (MMA) were synthesized in 1,4-dioxane using benzoyl peroxide as initiator at 70 ± 1 °C. The copolymers were analyzed by FTIR spectroscopy. The monomer reactivity ratios were determined by the methods of Fineman-Ross (F-R) and Kelen-Tudos (K-T), yielding the results r 1 (AcrNMP) = 0.552 and r 2 (MMA) = 1.074 by the F-R method and r 1 = 0.466 and r 2 = 0.980 by the K-T method. The latter r values in turn yielded Q = 0.56 and e = −0.49 for AcrNMP.

Structures of poly(ethylene propylene)–poly(ethylene oxide) (PEP–PEO) block copolymer micelles were determined from small-angle X-ray scattering and static light scattering and compared to predictions from a thermodynamic model. Both the corona block length and the solvent water–ethanol ratio were changed, leading to a thorough test of this model. With increasing ethanol fraction, the PEP core–solvent interfacial tension decreases, and the solvent quality for PEO changes. The weight-average block masses were 5.0 kDa for PEP and 2.8–49 kDa for PEO. For the lowest PEO molar mass and samples in pure water (except for the highest PEO molar mass), the micelles were cylindrical; for other conditions they were spherical. The structural parameters can be reasonably well described by the thermodynamic model by Zhulina et al. [Macromolecules2005, 38 (12), 5330–5351]; however, they have a stronger dependence on solvent composition and PEO molar mass than predicted.

Titanium dioxide (TiO