Development of nano-channel single crystals and verification of their structures by small angle X-ray scattering

Nano-channel single crystals were developed via consecutive growth of various polymer single-crystal channels comprising homo and block copolymers by self-seeding method. Poly(ethylene glycol)-b-polystyrene (PEG-b-PS) and poly(ethylene glycol)-b-poly(methyl methacrylate) (PEG-b-PMMA) block copolymers were synthesized by atom transfer radical polymerization. Self-seeding temperature, concentration, and crystallization time affected the width of the channels. This might provide a new way to investigate directional absorption, diffusion, and immobilization of biomacromolecules on the surface. The crystalline blocks of PEG-b-PS and PEG-b-PMMA diblock copolymers were similar, therefore, the continuity of channel-wire growth was guaranteed. Development of complete square channels next to the channels covered with high molecular weight brushes was infeasible. It was ascribed to a higher hindrance of primarily existing tethered chains on the single-crystal channel. Finally, the consecutive channel-wire single crystals were compared with single-step-grown pyramidal and conic structures. These multilayer crystals grew spirally and formed non-flat channels. The structure and morphology of different crystalline channels were detected by atomic force microscopy (AFM) and small angle X-ray scattering (SAXS). In this work, for the first time, the SAXS data of channel-wire single crystals were reported and they were compared by non-flat channel-like crystals. A profound investigation of PEG-b-PS, PEG-b-PMMA copolymers and PEG homopolymer channel-wire single crystals by SAXS and their comparison with AFM data was a novel work in the field of single-crystal engineering.     

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

     

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

     

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.     

A focus on the features of polyaniline nanofibres prepared via developing the single crystals of their block copolymers with poly(ethylene glycol)

Poly(ethylene glycol) (PEG)–polyaniline (PANI) diblock and triblock copolymers were synthesized via copolymerization of aniline with amine-terminated PEG by interfacial polymerization using sulphuric acid as dopant and ammonium peroxydisulfate (APS) as well as potassium hydrogen diiodate (PHD) as oxidants. The PHD-based synthesized PANI nanorods possessed longer lengths, narrower diameter distribution and higher conductivity. The electroactivity of synthesized copolymers was characterized using ultraviolet–visible (UV–Vis) spectrometry, cyclic voltammetry (CV) and resistivity measurement. Even in the presence of dielectric PEG blocks, the synthesized block copolymers had a conductivity around 3 S \(\hbox {cm}^{-1}\). In a further step, the solution-grown single crystals were prepared to investigate the general features of grafted PANI nanorods using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Based on AFM and SAXS analyses, the bimodal gel permeation chromatography (GPC) traces obtained from the block copolymers were originated from the diameter distribution of nanofibres, not from the dispersity of their lengths and molecular weights.     

Effect of miscibility on migration of third component in star‐like co‐continuous and disperse‐within‐disperse mixed brushes

Novel ternary mixed‐brush single crystals were designed with disperse‐within‐disperse and star‐like co‐continuous morphologies based on poly(ethylene glycol) (PEG)‐b‐polystyrene (PS)/PEG‐b‐poly(methyl methacrylate) (PMMA)/PEG‐b‐polyaniline (PANI) and PEG‐b‐PS/PEG‐b‐PMMA/PEG‐b‐(poly(?‐caprolactone) (PCL) or poly(l ‐lactide) (PLLA)) block copolymers, respectively. In the disperse‐within‐disperse ternary mixed brushes, PANI nanorods were dispersed within the matrix (PS)–dispersed (PMMA) amorphous brushes. The flexibility and rigidity of brushes mainly affected the ultimate morphology and arrangement of amorphous coiled brushes in the vicinity of PANI nanorods. In addition, the migration of PCL and PLLA crystallizable brushes was evident into PMMA phases dispersed in the PS matrix, leading to star‐like co‐continuous patterns of PCL and PLLA brushes. This phenomenon was related to the miscibility of crystallizable PCL and PLLA brushes with the PMMA phase. The migration of crystallizable PCL and PLLA brushes increased the size of PMMA domains in the star‐like co‐continuous patterns. Despite the larger osmotic pressure of PLLA brushes, their higher miscibility with PMMA chains reflected the greater PMMA dispersal and wider PLLA star‐like branches. © 2017 Society of Chemical Industry     

Three-dimensional macro/mesoporosity developments in polydimethylsiloxane

Macro/mesoporous polydimethylsiloxanes (PDMS) were prepared with the purpose of vascular grafts. Oligoester-containing semi-interpenetrating polymer networks (semi-IPNs) can be used as precursors for generation of networks with tunable pore sizes. Novel poly(methyl methacrylate)/PDMS semi-IPNs were prepared by varying structural parameters. Extraction of uncrosslinked oligoester subchains from semi-IPNs was investigated. To tailor the morphology of porous structure, influence of some factors including porogen type, different polymerization conditions, monomer type, and concentration, crosslinking agent concentration were studied. PDMS networks were examined by field emission scanning electron microscopy. A uniform porous structure with interconnected pores was detected in horizontal and vertical cross sections of PDMS.