Disperse-within-disperse patterning on ternary/binary mixed-brush single crystals using polyaniline,polystyrene and poly(methyl methacrylate) grafts

Novel binary rod-coil and ternary rod-coil-coil mixed-brushes were designed using poly(ethylene glycol) (PEG)-b-poly(styrene) (PS), PEG-b-poly(methyl methacrylate) (PMMA), and PEG-b-polyaniline (PANI) block copolymers. In the current rod-coil mixed-brushes, the brush osmotic pressure did not absolutely affect the surface morphology, instead, the rigidity or flexibility of brushes was a dominant factor. The flexibility of coily PS brushes caused them to be easily entered into the system compared to the rod brushes with higher osmotic pressure, thereby they composed the matrix phase. In a similar growth condition but with packed pancake PMMA brushes, a more faise osmotic pressure was detected for PANI nanorods in the vicinity of PMMA brushes compared to PS ones. A higher faise osmotic pressure for PANI nanorods reflected the lower diameter dispersity and population of PANI nanorods in PEG-b-PMMA/PEG-b-PANI compared to PEG-b-PS/PEG-b-PANI. Via enhancing the amorphous brushes molecular weight, in a constant PANI nanorods molecular weight, the diameter dispersity and population of PANI nanorods increased. The PANI nanorods diameter in binary PS/PANI and PMMA/PANI mixed-brushes ranged in 6–10 nm. With elevating the crystallization temperature, no changes were detected in the morphology of rod-coil mixed-brush single crystals. In the novel ternary mixed-brushes with the amorphous PS and PMMA brushes and the PANI nanorods, the PANI nanorods were dispersed within both matrix (PS) and disperse (PMMA) phases. In these systems, the PANI diameters were 6 and 7 nm in PMMA disperses and 6–9 nm in PS matrix phase. The overall PANI nanorods population was in the range of 594–1392 for binary mixed-brushes. Furthermore, in ternary structures, the PANI overall populations were about 222 and 316 in PMMA and PS phases, respectively. Generally, in all binary and ternary mixed-brush systems, the amorphous brushes (PS and PMMA), due to their flexibility could be arranged in the vicinity of each other in a more facile manner compared to the PANI nanorods, they thus developed matrix phase.

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Graphical abstract The mixed-brush single crystals were carefully patterned with double rod-coil and triple rod-coil-coil grafted polymer chains

     

The effect of reaction-induced micro-phase separation of block copolymer on curing kinetics of epoxy thermosets

The curing kinetics of epoxy system modified with Poly(ε-caprolactone)-block-Polystyrene (PCL-b-PS) diblock copolymer was investigated by differential scanning calorimetry(DSC). PCL-b-PS was synthesized Via the combination of ROP and ATRP, then incorporated into epoxy to access the nanostructured thermosets. The results of TEM, SAXS and DSC demonstrated the occurrence of Reaction-induced Micro-phase Separation. Kinetic studies showed that the PCL-b-PS block copolymer delayed the curing reactions of epoxy system. The occurrence of Reaction-induced Micro-phase Separation had no significant effect on the total heat of reaction ?H and the total activation energy, but resulted in a higher activation energy at the beginning of curing. The increase in activation energy at the initial stage of curing was related to the size and distribution of the dispersed phase. It is expected that the investigation of cure kinetics of EP/PCL-b-PS could provide more theoretical basis for the preparation of block copolymer modified epoxy resin.     

Synthesis of all-acrylic graft copolymers by grafting-through strategy in emulsion

In this paper, PnBA-g-PMMA brush-like and centipede multigraft copolymers were synthesized via DPE seeded emulsion polymerization and miniemulsion polymerization. PMMA macromonomers with single tail and double tails were prepared by DPE-technique in emulsion and Steglich esterification. Then PnBA-g-PMMA multigraft copolymers were obtained by miniemulsion copolymerization. The molecular weight and polydispersity indices of PMMA macromonomers and graft copolymers were characterized by GPC. The structural characteristics, weight content of PMMA and the number of grafting sites in brush-like and centipede multigraft copolymers were determined by ¹H NMR. The thermal performance of graft copolymers were analyzed by DSC and TGA. AFM confirmed microphase separation between PnBA block and PMMA block.     

Preparation of pH-sensitive amphiphilic block star polymers,their self-assembling characteristics and release behavior on encapsulated molecules

Poly(ethylene glycol) (PEG), a polymer with excellent biocompatibility, was widely used to form nanoparticles for drug delivery applications. In this paper, based on PEG, a series of pH-sensitive amphiphilic block star polymers of poly(ethylene glycol)-block-poly(ethoxy ethyl glycidyl ether) (PEG-b-PEEGE) with different hydrophobic length were synthesized by living anionic ring-opening polymerization method. The products were characterized using ¹H NMR and gel permeation chromatography. These copolymers could self-assemble in aqueous solution to form micellar structure with controlled morphologies. Transmission electron microscopy showed that the nanoparticles are spherical or rodlike with different hydrophilic mass fractions. The pH response of polymeric aggregates from PEG-b-PEEGE was detected by fluorescence probe technique at different pH. A pH-dependent release behavior was observed and pH-responsiveness of PEG-b-PEEGE was affected by the hydrophobic block length. These results demonstrated that star-shaped polymers (PEG-b-PEEGE) are attractive candidates as anticancer drug delivery carriers.     

Reaction-induced microphase separation in thermosetting blends of epoxy resin with poly(methyl methacrylate)-block-polystyrene block copolymers: Effect of topologies of block copolymers on morphological structures

Polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymers with linear and tetra-armed star-shaped topological structures were synthesized via sequential atomic transfer radical polymerization (ATRP). With pentaerythritol tetrakis(2-bromoisobutyrate) as the initiator, the star-shaped block copolymers with two sequential structures (i.e., s-PMMA-b-PS and s-PS-b-PMMA) were prepared and the arm lengths and composition of the star-shaped block copolymers were controlled to be comparable with those of the linear PS-b-PMMA (denoted as l-PS-b-PMMA). The block copolymers were incorporated into epoxy resin to access the nanostructures in epoxy thermosets, by knowing that PMMA is miscible with epoxy after and before curing reaction whereas the reaction-induced phase separation occurred in the thermosetting blends of epoxy resin with PS. Considering the difference in miscibility of epoxy with PMMA and/or PS, it is judged that the reaction-induced microphase separation occurred in the systems. The design of these block copolymers allows one to investigate the effect of topological structures of block copolymers on the morphological structures of the thermosets. By means of atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS), the morphology of the thermosets was examined. It is found that the nanostructures were formed in the thermosets containing l-PMMA-b-PS and s-PS-b-PMMA block copolymers. It is noted that the long-range order of the nanostructures in the epoxy thermosets containing l-PMMA-b-PS is obviously higher than that in the system containing s-PS-b-PMMA. However, the macroscopic phase separation occurred in the thermosetting blends of epoxy resin with s-PMMA-b-PS block copolymer.     

Structure and sorption properties of hypercrosslinked polystyrenes and magnetic nanocomposite materials based on them

Some special habits of dilute solution-grown single crystals were introduced by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM) equipped with electron diffraction (ED). Well-defined block copolymers of poly(ethylene glycol)-block-polystyrene (PEG-b-PS) having predetermined molecular weight and narrow molecular weight distribution (1.06–1.08) were synthesized by atom transfer radical polymerization (ATRP). The single crystals of PEG-b-PS copolymers were grown in a mixed solvent comprised of chlorobenzene/octane and separately in amyl acetate, both using a self-seeding technique. We were capable to develop various growth fronts that resulted from different growth rates through infinitesimal temperature fluctuations. Elevated crystallization temperatures and a higher ratio of molecular weight of PS to that of PEG intensified the curvatures. The corresponding overall, crystalline, and amorphous thickness of a given single crystal, either in square and truncated shapes or with concave and convex lateral sides, had high consistency with each other.     

Micellization and sol-gel transition of novel thermo- and pH-responsive ABC triblock copolymer synthesized by RAFT

A well-defined thermo- and pH-responsive ABC-type triblock copolymer monomethoxy poly(ethylene glycol)-b-poly(2-(2-methoxyethoxy) ethyl methacrylate-co-N-hydroxymethyl acrylamide)-b-poly(2-(diethylamino) ethyl methacrylate), mPEG-b-P(MEO₂MA-co-HMAM)-b-PDEAEMA, was synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT). The ABC-type triblock copolymer was endowed thermo- and pH-responsive, corresponding to the thermosensitive properties of P(MEO₂MA-co-HMAM) and pH-responsive properties PDEAEMA segments, respectively. The thermo- and pH-responsive properties of copolymer aqueous solutions were studied by UV transmittance measurements, dynamic light scattering (DLS), transmission electron microscopy (TEM). The results showed that the N-hydroxymethyl acrylamide (HMAM) content in triblock copolymer affected the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution. The copolymer self-assembled into core-shell micelles, with the thermoresponsive P(MEO₂MA-co-HMAM) block and the hydrophilic PEG block as the shell, the hydrophobic PDEAEMA block as the core, in alkaline solution at room temperature. While in acidic media, when the temperature above the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution, the copolymer self-assembled into P(MEO₂MA-co-HMAM)-core micelles with mixed hydrophilic PEG and pH-responsive PDEAEMA coronas. Sol-gel transition temperature (T_sol-gel) for the triblock copolymer determined by vial inversion test further indicated that it is dependent on the concentration of the triblock copolymers and solution pH. Copolymer hydrogel loaded with bovine serum albumin (BSA) were used for the sustained release study. The results indicated that the hydrogel was a promising candidate for controlling protein drug delivery.     

Preparation of polymer brushes via growth of single crystals of poly(ethylene glycol)-block-polystyrene diblock copolymers synthesized by ATRP and studying the crystal lateral size and brush tethering density

Well-defined block copolymers of poly(ethylene glycol)-block-polystyrene (PEG-b-PS) were synthesized by atom transfer radical polymerization with predetermined molecular weights and narrow molecular weight distributions (1.06–1.08). The single crystals of PEG-b-PS copolymers were grown in chlorobenzene/octane mixed theta solvent using self-seeding technique. The effect of self-seeding temperature (T _s) on single crystal lateral size was evaluated. The atomic force microscopy (AFM) height images were indicative of increasing the single crystal lateral sizes, which were of several microns, via elevating T _s. The non-ideal structures were increasing by moving away from the optimized T _s (41.5 °C). Here, we studied the transition point between non-interaction and interaction regimes in a mixed theta solvent for PS as well. The impact of the PS block hindrance and the influence of crystallization temperature on thickness, tethering density and reduced tethering density of PS brushes were also investigated. Although these factors did not have the same effect on thickness and tethering density, the trend of their influence on reduced tethering density was the same. The results were recognized by AFM, transmission electron microscopy and small angle X-ray scattering.     

Synthesis of poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene triblock copolymers by two-step atom transfer radical polymerization

The synthesis of ABC triblock copolymer poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene (PEO-b-PMMA-b-PS) via atom transfer radical polymerization (ATRP) is reported. First, a PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide, which was subsequently used in the preparation of halo-terminated poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymers under ATRP conditions. Then PEO-b-PMMA-b-PS triblock copolymer was synthesized by ATRP of styrene using PEO-b-PMMA as a macroinitiator. The structures and molecular characteristics of the PEO-b-PMMA-b-PS triblock copolymers were studied by FT-IR, GPC and ¹H NMR.     

A delicate maneuver on conjugated rod-rod structures composed of poly(3-hexylthiophene) and polyaniline subtending patched-fibrillar,ringed-fibrillar,double-fibrillar and sandwiched configurations

Full-conjugated rod-rod structures comprising patched-fibrillar, ringed-fibrillar, and double-fibrillar configurations were designed from poly(3-hexylthiophene) (homo-P3HT) and polyaniline (PANI) nanorods in chloroform, p-xylene, and amyl acetate dilute solutions, respectively. Solvent quality, seeding effect, and constituent material were focused while characterizing the developed structures. By exacerbating the processing solvent quality from chloroform to p-xylene, a ringed-fibrillar configuration was detected instead of patched-fibrillar structure. In a poor solvent, double-fibrillar structures were acquired from homo-P3HT chains and PANI nanorods. Towards a poorer solvent, P3HT chains were capable of developing their own crystals by less sensing presence of PANI nanorods as seeds. In another experiment, by copolymerization of both P3HT and PANI with crystallizable PEG blocks, sandwiched rod-rod mixed-brush single crystals were developed. Molecular weight of neither P3HT nor PANI was effective on surface patterning of P3HT/PANI mixed-brushes. Via elevating crystallization temperature, PANI dispersed patterns became more delicate and their width decreased from 80 to 160 nm to 12–30 nm. P3HT backbones were tethered with a extended flat-on orientation onto the PEG substrate at either low or high crystallization temperatures. Beside sandwiched single crystals seeded with homo-PEG tiny crystals, slightly and highly curved half-ring crystals were also developed in the PEG-b-P3HT systems.

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Graphical abstract

     

Crystallinity of large single crystals of FAU-type zeolites with a wide range of Si/Al ratios

Large colorless single crystals of FAU-type zeolites were synthesized from gels with the composition xSiO₂ : 2.0NaAlO₂ : 7.5NaOH : 454H₂O : 5.0TEA, where x = 2.0–6.0. FAU-type zeolite with Si/Al = 1.26(4) was nearly pure and the maximum size of the single crystals was ca. 150 μm. In case of FAU-type zeolites with Si/Al = 1.54(5), the maximum size of single crystals was ca. 200 μm and the ratio of FAU/impurity was 0.07. The framework Si/Al ratio of the as-synthesized FAU-type zeolite tended to increase with the Si/Al ratio of gel composition. All of the large single crystals had good crystallinities for single-crystal X-ray diffraction, leading to enough numbers of significant reflections which have strong intensity. The structure of a single crystal of dehydrated zeolite Na-X (Si/Al = 1.41(4)) with composition |Na₈₀|[Si₁₁₂Al₈₀O₃₈₄]-FAU per unit cell was determined by X-ray diffraction methods in the cubic space group \( Fd \bar{3} m; \) a = 24.9434(6) Å at 294 K. The structure was refined by using all intensities to the final error indices (using only the 771 reflections for which F _o > 4σ(F _o)), R ₁ = 0.048 (based on F) and R ₂ = 0.188 (based on F ²). In the crystallographic studies, the Si/Al ratio of the synthetic FAU-type zeolite is 1.41(4) which is quite consistent with the SEM–EDS analysis.     

Effect of different structured POSS/GMA-containing copolymers on the morphology of porous coating by breath-figures method

Polyhedral oligomeric silsesquioxane (POSS) and glycidyl methacrylate (GMA) are used to synthesize linear L-(PGMA-b-MA-POSS), dicephalous D-(PGMA-b-MA-POSS)₂, and four-armed T-(PGMA-b-MA-POSS)₄ through atom transfer radical polymerization (ATRP). These different structured POSS/GMA-containing copolymers are applied to build the porous films through breath-figures (BF) method. L-(PGMA-b-MA-POSS) is easy to form the ordered porous BF film, and T-(PGMA-b-MA-POSS)₄ tends to form well-distributed BF film due to its high segment density which is beneficial to stabilize water drop. It is proven that solvent has a great effect on the morphologies of BF film. The perfect BF film is developed in the relatively wet atmosphere as 5–8 μm diameter of pores casted in THF and 2–4 μm diameter of pores casted in CH₂Cl₂ with regular morphology. The developed BF film has superior stability than the film developed in natural conditions due to the shorter stable balancing time. Therefore, it is believed that the obtained porous films show great potential in coating application.     

Mesostructure controllable ZSM-5 single crystals supported Pd/transition metal oxides: efficient and reusable catalysts for selective oxidation under aerobic conditions

Pd and transition metal oxides functionalized ZSM-5 single crystals with b-axis aligned mesopores (ZSM-5-OM-PdO _x -MO _x ) were prepared. ZSM-5-OM support was obtained from crystallization of aluminosilicate gels in the presence of cationic polymers. Characterizations indicate abundant nanopores and highly crystalline degree of ZSM-5-OM-PdO _x -MO _x , and active species of Pd and transition metals were homogeneously dispersed into ZSM-5-OM, which showed unique interactions and enhanced ability for activating oxygen. Catalytic tests showed that ZSM-5-OM-PdO _x -MO _x were highly active and reusable catalysts for selective oxidation of alcohols under aerobic and solvent free condition, which were much better than those of Pd/transition metal oxides functionalized ZSM-5, mesoporous silica of SBA-15, and activated carbon catalysts.     

Reinforcement effect of poly (methyl methacrylate)-<Emphasis Type="Italic">g</Emphasis>-cellulose nanofibers on LDPE/thermoplastic starch composites: preparation and characterization

The effect of cellulose nanofibers (CNFs) and poly [methyl methacrylate (MMA)]-grafted cellulose nanofibers (CNF-g-PMMA) on mechanical properties and degradability of a 75/25 low density polyethylene/thermoplastic starch (LDPE/TPS) blend was investigated. Graft copolymerization on CNFs was performed in an aqueous suspension by free radical polymerization using MMA as an acrylic monomer. In addition, a LDPE/TPS blend was reinforced by different amounts of CNFs (1–5 wt%) and CNF-g-PMMA (1–7 wt%) using a twin-screw extruder. A 61% grafting of PMMA on the surface of CNFs was demonstrated by gravimetric analysis. Moreover, after modification the X-ray photoelectron spectroscopy analysis showed a 20% increase of carbon atoms on the surface of CNFs and a 22.6% decrease in the oxygen content of its surface. The mechanical properties of the CNFs-modified composites were significantly improved compared to the unmodified nanocomposites. The highest tensile strength and Young’s modulus were obtained for the composites reinforced by 3 and 7 wt% CNF-g-PMMA, respectively. The degradability of cellulose nanocomposites was studied by water absorption and soil burial tests. Surface modification of CNFs lowered water absorption, and soil burial test of the LDPE/TPS blend showed improvement in biodegradability by addition of CNF-g-PMMA.     

Core/shell morphologies in recycled poly(ethylene terephthalate)/linear low-density polyethylene/poly(styrene-<Emphasis Type="Italic">b</Emphasis>-(ethylene-<Emphasis Type="Italic">co</Emphasis>-butylene)-<Emphasis Type="Italic">b</Emphasis>-styrene) ternary blends

Compatibilizer plays very important roles in preparing high performance polymer composites, not only for the ternary immiscible polymer blends, but also for the recycled and reused of waste plastics mixture. Generally, the compatibilizers can be used as the toughening agent in blending polymer materials. In the present work, the poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) or maleic anhydride-grafted poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS-g-MA) acts as the compatibilizer and toughening agent for the preparation of R-PET/LDPE/SEBS (70/20/10) ternary blends. It must be pointed that the ternary blends are costlessly and conveniently prepared from the recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) through a melt blending in a co-rotating twin-screw extruder and injection moulded. The morphologies of the ternary blends are characterized by scanning electron microscopy (SEM). It was found that the blends contains reactive or non-reactive compatibilizer, the morphology originates from the LLDPE particles encapsulated by both SEBS and SEBS-g-MA. So, it results to the reduced interfacial tension between of the R-PET and SEBS-g-MA, in which the grafted chains of PET-g-SEBS-g-MA formed through in situ reaction between R-PET and SEBS-g-MA phases. Therefore, core–shell particles with smaller diameter disperse uniformly in the blends. Moreover, the good compatibilization and corresponding morphologies induce in balanced mechanical and thermal properties. DSC analysis show the dispersed phase particles could act as nucleating agent in the R-PET matrix, which results the improvement of the crystallization temperature. And it was also observed the decreased nucleation activity in graft copolymers in the R-PET/LLDPE/SEBS-g-MA blends. Notched Charpy impact strength and elongation at break are improved by the addition of compatibilizer.     

Novel amphiphilic temperature responsive graft copolymers PCL-<Emphasis Type="Italic">g</Emphasis>-P(MEO<Subscript>2</Subscript>MA-<Emphasis Type="Italic">co</Emphasis>-OEGMA) via a combination of ROP and ATRP: synthesis,characterization, and sol-gel transition

A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO₂MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by ¹H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO₂MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10^?3, 9.1 × 10^?4 and 1.5 × 10^?3 mg·mL^?1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.     

A new method in designing compatibility and adhesion of EVA/PMMA blend by using EVA-<Emphasis Type="Italic">g</Emphasis>-PMMA with controlled graft chain length

Atom transfer free radical polymerization (ATRP) was employed in a synthesis of graft polymer EVA-g-PMMA with controlled length of side PMMA chains. Three steps of synthesis: partial hydrolysis of EVA, esterification with chloroacetyl chloride and ATRP grafting were performed to produce EVAOH, macroinitiator EVACl and grafted polymers G8020 (EVA/PMMA?=?80/20 wt%) and G6040 (EVA/PMMA?=?60/40 wt%). FTIR, Raman and NMR spectroscopy were used in the determination of the chemical structure and modification of EVA. Transmitted light and dark field microscopy showed higher affinity for coil formation of EVA-g-PMMA with longer PMMA side chains, i.e. G6040 compatibilizer. Morphological, thermal and adhesive properties of optical fiber adhesives of graft polymers and polymer blends poly(ethylene-co-vinyl acetate)-blend-poly(methyl methacrylate) (EVA/PMMA) compatibilized with 1 wt% of EVA-g-PMMA, were studied. Image analysis of SEM micrographs showed effective compatibilization with short grafted chains (G8020) that was indicated by lower porosity characteristics. TG/DTG analysis enabled determination of degree of hydrolysis and amount of chloro-functionalized groups. DSC analysis showed higher thermal stability of G8020 polymer. Single lap joint of adhesives/optical fibers were subjected to adhesive testing and obtained results for maximal force applied and adhesive failure suggested the visible influence of the length of graft chains on adhesion.     

Novel hybrid block copolymer nanocarrier systems to load lipophilic drugs prepared by microphase inversion method

Nanoparticles based on block copolymers of oligosaccharides [β-cyclodextrin (βCyD) and maltoheptaose (Mal₇)] and poly(ε-caprolactone) (PCL) were prepared by microphase inversion method. Zeta-potential, particle size measurements and morphological analysis of drug-free and drug-loaded nanoparticles were performed by using, respectively, laser-doppler anemometry, dynamic and static light scattering and transmission electron microscopy. ρ-Ratio values were correlated with transmission electron microscopy observations. Both types of amphiphilic block copolymers, βCyD-b-PCL_5k and Mal₇-b-PCL_5k, self-assembled in water to form spherical vesicles, presented a hydrodynamic diameter of 72 and 34 nm, respectively. The incorporation of drugs into nanoparticles did not affect significantly the particle size for βCyD-b-PCL_5k-based nanoparticles with progesterone, unlike the other tested systems. On the other hand, all nanoparticles (with and without drug) were negatively charged. Both nanoparticulate systems showed high drug loading efficiency (higher than 95%), confirming their suitability as delivery system for lipophilic drugs.     

Structure of sulfur complexes in zeolite Na<Emphasis Type="Italic">X</Emphasis>(S)

The distribution of sulfur atoms embedded in single crystals of zeolite NaX is investigated using the single-crystal X-ray diffraction analysis. It is shown that, in the unit cell of the NaX(S) zeolite, 67 sulfur atoms are located in the form of S₈ or S₆ rings and S₂ molecules in large cavities and in the form of Na₄S₄ complexes in the sodalite cages.     

Synthesis of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-<Emphasis Type="Italic">b</Emphasis>-<Emphasis Type="Italic">N</Emphasis>-vinylcarbazole) copolymers via RAFT polymerization and its stimuli responsive morphology in aqueous media

Here, we report the successful synthesis of series of stimuli responsive amphiphilic diblock copolymers (SRABCs) poly(N-isopropylacrylamide-b-N-vinylcarbazole) [poly(NIPAAm-b-NVK)] through reversible addition fragmentation chain transfer (RAFT) polymerization. Copolymers with fixed hydrophilic [poly(NIPAAm)] block length and variable (with three different) hydrophobic [poly(NVK)] block lengths were synthesized and the block length ratio was confirmed from their molecular weight data. The self-assembly nature of synthesized block copolymers was confirmed by determining critical micelle concentration (CMC). Self-assembled block copolymers showed rice-grain like morphology for copolymers having equivalent hydrophobic/hydrophilic chain length but in case of block copolymers having smaller and bigger hydrophobic chain length with respect to hydrophilic chain length displayed vesicular morphology. The thermo and pH responsiveness of the block copolymers was found to be influenced by variation in length and chemical composition of the blocks. Due to their thermo and pH responsiveness resulted self-assembled structures underwent morphology transitions from vesicular and rice grain like to micellar structure in aqueous medium. The probable applications of the studied stimuli responsive amphiphilic diblock copolymers can be found in the nanotechnology and biotechnology are indicated.

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Graphical abstract Synthesis, self-assembly and stimuli responsiveness of poly(NIPAAm-b-NVK) copolymers.