Stiff Shape Memory Polymers for High-Resolution Reconfigurable Nanophotonics.

Reconfigurable metamaterials require constituent nanostructures to demonstrate switching of shapes with external stimuli. Yet, a longstanding challenge is in overcoming stiction caused by van der Waals forces in the deformed configuration, which impedes shape recovery. Here, we introduce stiff shape memory polymers. This designer material has a storage modulus of ∼5.2 GPa at room temperature and ∼90 MPa in the rubbery state at 150 °C, 1 order of magnitude higher than those in previous reports. Nanopillars with diameters of ∼400 nm and an aspect ratio as high as ∼10 were printed by two-photon lithography. Experimentally, we observe shape recovery as collapsed and touching structures overcome stiction to stand back up. We develop a theoretical model to explain the recoverability of these sub-micrometer structures. Reconfigurable structural color prints with a resolution of 21150 dots per inch and holograms are demonstrated, indicating potential applications of the stiff shape memory polymers in high-resolution reconfigurable nanophotonics.

Bioactivity of porous biphasic calcium phosphate enhanced by recombinant human bone morphogenetic protein 2/silk fibroin microsphere.

To prepare a bioactive bone substitute, which integrates biphasic calcium phosphate (BCP) and rhBMP-2/silk fibroin (SF) microsphere, and to evaluate its characteristics. Hydroxyapatite and ß-tricalcium phosphate were integrated with a ratio of 60­40%. RhBMP-2/SF (0.5 µg/1 mg) microsphere was prepared, and its rhBMP-2-release kinetics was assed. After joining pore-forming agent (Sodium chloride, NaCl), porous BCP/rhBMP-2/SF were manufactured, and its characteristics and bioactivity in vitro were evaluated. Mean diameter of rhBMP-2/SF microsphere was 398.7 ± 99.86 nm, with a loading rate of 4.53 ± 0.08%. RhBMP-2 was released in a dual-phase pattern, of which fast-release (nearly half of protein released) focused on the initial 3 days, and slow-release sustained more than 28 days. With the increase in concentration of NaCl, greater was porosity and pore size, but smaller mechanical strength of BCP/rhBMP-2/SF. Material with 150% (w/v) NaCl had an optimal performance, with a porosity of 78.83%, pore size of 293.25 ± 42.77µm and mechanical strength of 31.03 MPa. Proliferation of human placenta-derived mesenchymal stem cells (hPMSCs) on leaching extract medium was similar to the normal medium (P = 0.89), which was better than that on control group (P = 0.03). Activity of alkaline phosphatase on BCP/rhBMP-2/SF surface was higher than on pure BCP at each time point except at 1 day (P < 0.05). RhBMP-2 has a burst release on early times and a sustaining release on later times. BCP/rhBMP-2/SF with 150% (w/v) pore-forming agent has excellent porosity, pore size and mechanical strength. The biomaterial induces proliferation and differentiation hPMSCs effectively.

Surfactant-assisted preparation of all-gel-state flexible supercapacitor with remarkable electrochemical performance based on polyaniline-polyacrylamide/sodium alginate hydrogels.

The electrochemical performance of polyaniline-based all-gel-state supercapacitor (AGSSC) is significantly depended on the dispersity and mass loaded of polyaniline (PANI). In this manuscript, inspired by the properties of surfactant, sodium dodecylbenzene sulfonate (SDBS) was introduced to prepare various PANI-polyacrylamide/sodium alginate/SDBS (PANIy-PSSx) AGSSCs. With presence of SDBS, the electrochemical performance of PANIy-PSSx AGSSCs was greatly improved, displaying a trend of initial rise and then decrease with increasing concentration of SDBS from 0 to 0.75 wt%. As the content of SDBS was 0.5 wt%, the resulting PANI1.0-PSS0.5 AGSSC displayed the optimum electrochemical properties with area capacitance and energy density of 913.79 mF/cm2 and 81.23 µWh/cm2, respectively. The capacitance rate of PANI1.0-PSS0.5 AGSSC was still more than 93 % after 2000 cycles of sequential CV scans at the scan rate of 200 mV/s. These data were greatly higher than many reported PANI-based AGSSCs. Moreover, the resultant PANI1.0-PSS0.5 AGSSC could maintain high electrochemical performance even after various operations, such as compression, puncture, fluctuating temperature, bending situations and various voltage windows and series-parallel connections. The resultant PANI1.0-PSS0.5 AGSSC had the wide potentials to satisfy the real application requirements. This study offered a facile strategy for design and preparation of flexible supercapacitor with excellent electrochemical performance.

Haloarchaeal-type ß-ketothiolases involved in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) synthesis in Haloferax mediterranei.

The key enzymes for poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) biosynthesis in haloarchaea have been identified except the ß-ketothiolase(s), which condense two acetyl coenzyme A (acetyl-CoA) molecules to acetoacetyl-CoA, or one acetyl-CoA and one propionyl-CoA to 3-ketovaleryl-CoA. Whole-genome analysis has revealed eight potential ß-ketothiolase genes in the haloarchaeon Haloferax mediterranei, among which the PHBV-specific BktB and PhaA were identified by gene knockout and complementation analysis. Unlike all known bacterial counterparts encoded by a single gene, the haloarchaeal PhaA that was involved in acetoacetyl-CoA generation, was composed of two different types of subunits (PhaAα and PhaAß) and encoded by the cotranscribed HFX_1023 (phaAα) and HFX_1022 (phaAß) genes. Similarly, the BktB that was involved in generation of acetoacetyl-CoA and 3-ketovaleryl-CoA, was also composed of two different types of subunits (BktBα and BktBß) and encoded by cotranscribed HFX_6004 (bktBα) and HFX_6003 (bktBß). BktBα and PhaAα were the catalytic subunits and determined substrate specificities of BktB and PhaA, respectively. Their catalytic triad "Ser-His-His" was distinct from the bacterial "Cys-His-Cys." BktBß and PhaAß both contained an oligosaccharide-binding fold domain, which was essential for the ß-ketothiolase activity. Interestingly, BktBß and PhaAß were functionally interchangeable, although PhaAß preferred functioning with PhaAα. In addition, BktB showed biotechnological potential for the production of PHBV with the desired 3-hydroxyvalerate fraction in haloarchaea. This is the first report of the haloarchaeal type of PHBV-specific ß-ketothiolases, which are distinct from their bacterial counterparts in both subunit composition and catalytic residues.

Multiple propionyl coenzyme A-supplying pathways for production of the bioplastic poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in Haloferax mediterranei.

Haloferax mediterranei is able to accumulate the bioplastic poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with more than 10 mol% 3-hydroxyvalerate (3HV) from unrelated carbon sources. However, the pathways that produce propionyl coenzyme A (propionyl-CoA), an important precursor of 3HV monomer, have not yet been determined. Bioinformatic analysis of H. mediterranei genome indicated that this strain uses multiple pathways for propionyl-CoA biosynthesis, including the citramalate/2-oxobutyrate pathway, the aspartate/2-oxobutyrate pathway, the methylmalonyl-CoA pathway, and a novel 3-hydroxypropionate pathway. Cofeeding of pathway intermediates and inactivating pathway-specific genes supported that these four pathways were indeed involved in the biosynthesis of 3HV monomer. The novel 3-hydroxypropionate pathway that couples CO2 assimilation with PHBV biosynthesis was further confirmed by analysis of (13)C positional enrichment in 3HV. Notably, (13)C metabolic flux analysis showed that the citramalate/2-oxobutyrate pathway (53.0% flux) and the 3-hydroxypropionate pathway (30.6% flux) were the two main generators of propionyl-CoA from glucose. In addition, genetic perturbation on the transcriptome of the ΔphaEC mutant (deficient in PHBV accumulation) revealed that a considerable number of genes in the four propionyl-CoA synthetic pathways were significantly downregulated. We determined for the first time four propionyl-CoA-supplying pathways for PHBV production in haloarchaea, particularly including a new 3-hydroxypropionate pathway. These results would provide novel strategies for the production of PHBV with controllable 3HV molar fraction.

Complete genome sequence of the metabolically versatile halophilic archaeon Haloferax mediterranei, a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) producer.

Haloferax mediterranei, an extremely halophilic archaeon, has shown promise for production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) from unrelated cheap carbon sources. Here we report the complete genome (3,904,707 bp) of H. mediterranei CGMCC 1.2087, consisting of one chromosome and three megaplasmids.

Effects of additive dosage and coagulation bath pH on amphoteric fluorocarbon special surfactant (FS-50) blend PVDF membranes.

Amphiphilic copolymers containing hydrophilic and hydrophobic blocks represented by surfactants have proven to be more effective for modifying membranes than hydrophilic copolymers. However, studies on the effects of additive and coagulation bath pH on the morphology and properties of surfactant-modified membranes have rarely been reported. Hence, this study aims to investigate the effects of the additive dosage and the coagulation bath pH on the mechanisms of phase inversion and performance improvement of amphoteric fluorocarbon special surfactant (FS-50) blended PVDF membranes. It was observed that the pure water flux increased from 114.68 LMH/bar of the original membrane M0 to 205.02 LMH/bar of the blend membrane M1, and then to 615.88 LMH/bar of the coagulation-bath-regulated membrane MPH9 with a high BSA rejection rate of 90.86%, showing a two-stage jump. The addition of FS-50 promoted the instantaneous phase inversion of the membrane, allowing the blend membrane to exhibit a higher proportion of pore characteristics and stronger permeability. After that, the mechanisms of the membrane phase inversion process affected by the coagulation bath pH were interpreted according to the pH-response characteristics of FS-50 in terms of charge repulsion effect and compressed double-electron layer effect. Furthermore, the cross-sectional morphology and the surface structure of the membrane prepared in acidic and alkaline coagulation baths were significantly affected by the pH of the coagulation bath, exhibiting different features. For one, the porosity of the membranes gradually decreased as the acidity and alkalinity of the coagulation bath increased, and the membrane MPH9 exhibited both maximum surface and overall porosity. For another, the coagulation bath pH did not negatively affect the contact angle, surface roughness and tensile strength of the membranes. Overall, adjusting the dosage of FS-50 and the pH of the coagulation bath is a promising approach to greatly enhance membrane performance.

Eco-friendly flame retardant and dripping-resistant of polyester/cotton blend fabrics through layer-by-layer assembly fully bio-based chitosan/phytic acid coating.

Polyester/cotton blend fabrics are widely used in clothing and household textiles which combine the comfort of cotton and excellent mechanical strength of polyester. However, their high flammability due to the special "wick effect" resulting from the different thermal decomposition process of cotton and polyester causes greatly potential fire hazards. In this study, fully bio-based intumescent flame retardant (IFR) coating of chitosan/phytic acid (CS/PA) was layer-by-layer (LBL) assembly constructed on polyester/cotton blend fabrics. The LOI value of polyester/cotton blend fabric which was LBL assembly coated by 20 bilayers CS/PA reached 29.2%. And the dripping of coated fabric was eliminated. The results of cone calorimetry test confirmed CS/PA coating greatly improved the flame retardancy of polyester/cotton blend fabrics. Thermogravimetric analysis (TGA) results showed CS/PA coating changed the thermal decomposition process to promote the char formation of polyester/cotton blend fabrics. CS/PA coating on fabric could form the IFR system which acts through both condensed phase action by the catalysis dehydration reaction to forming stable char and gas phase action by the blowing effect. This research provides a new strategy to eco-friendly flame retardant and dripping-resistant for polyester/cotton blend fabrics by bio-based IFR system through facile LBL assembly method.

Wide distribution among halophilic archaea of a novel polyhydroxyalkanoate synthase subtype with homology to bacterial type III synthases.

Polyhydroxyalkanoates (PHAs) are accumulated as intracellular carbon and energy storage polymers by various bacteria and a few haloarchaea. In this study, 28 strains belonging to 15 genera in the family Halobacteriaceae were investigated with respect to their ability to synthesize PHAs and the types of their PHA synthases. Fermentation results showed that 18 strains from 12 genera could synthesize polyhydroxybutyrate (PHB) or poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). For most of these haloarchaea, selected regions of the phaE and phaC genes encoding PHA synthases (type III) were cloned via PCR with consensus-degenerate hybrid oligonucleotide primers (CODEHOPs) and were sequenced. The PHA synthases were also examined by Western blotting using haloarchaeal Haloarcula marismortui PhaC (PhaC(Hm)) antisera. Phylogenetic analysis showed that the type III PHA synthases from species of the Halobacteriaceae and the Bacteria domain clustered separately. Comparison of their amino acid sequences revealed that haloarchaeal PHA synthases differed greatly in both molecular weight and certain conserved motifs. The longer C terminus of haloarchaeal PhaC was found to be indispensable for its enzymatic activity, and two additional amino acid residues (C143 and C190) of PhaC(Hm) were proved to be important for its in vivo function. Thus, we conclude that a novel subtype (IIIA) of type III PHA synthase with unique features that distinguish it from the bacterial subtype (IIIB) is widely distributed in haloarchaea and appears to be involved in PHA biosynthesis.

[Identification of the phaB genes and analysis of the PHBV precursor supplying pathway in Haloferax mediterranei].

OBJECTIVE: Identification and characterization of the genes involved in precursor supplying for poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) biosynthesis in the haloarchaeon Haloferax mediterranei. METHODS: By using BLAST (Basic Local Alignment Search Tool) search methodology, we obtained five genes (phaB1, phaB2, phaJ1, phaJ2 and phaJ3) that were possibly involved in the 3-hydroxyacyl-CoA precursor supplying for PHBV biosynthesis in H. mediterranei. Firstly, we proved that these five genes were all transcribed under the PHBV-accumulating condition in H. mediterranei. Then, we knocked out these genes individually or in combination, by double-crossover homologous recombination, resulting in the following mutants: deltaphaB1, deltaphaB2, AphaJ1, deltaphaJ2, deltaphaJ3, deltaphaB1phaB2, deltaphaJ1phaJ2 and deltaphaJ1phaJ2phaJ3. Finally, we performed the complementation analysis of the deltaphaB1phaB2 strain, with the phaB1 and phaB2 genes, respectively. RESULTS: Whenever the three phaJ genes were knocked out individually or in combination, there was no obvious influence on PHBV accumulation in H. mediterranei. Knockout of phaB1 also did not affect the PHBV accumulation obviously. However, when phaB2 was knocked out, the yield of PHBV and the fraction of the 3-HV monomer decreased significantly. Notably, when the phaB1 and phaB2 were knocked out in combination, the CONCLUSIONS: The PHBV-specific acetoacetyl-CoA reductases mutant deltaphaB1phaB2 no longer produced PHBV. (PhaB) involved in the precursor supplying for PHBV biosynthesis are encoded by phaB1 and phaB2 in H. mediterranei.

Fabrication and characterization of conductive poly (3,4-ethylenedioxythiophene) doped with hyaluronic acid/poly (l-lactic acid) composite film for biomedical application.

Poly 3,4-ethylenedioxythiophene (PEDOT), a polythiophene derivative, has been proved to be modified by chemical process as biocompatible conductive polymer for biomedical applications. In this study, novel hyaluronic acid (HA)-doped PEDOT nanoparticles were synthesized by the method of chemical oxidative polymerization, then conductive PEDOT-HA/poly(l-lactic acid) (PLLA) composite films were prepared. The physicochemical characteristics and biocompatibility of films were further investigated. FTIR, Raman and EDX analysis demonstrated that HA was successfully doped into PEDOT particles. Cyclic voltammograms indicated PEDOT-HA particles had favorable electrochemical stability. PEDOT-HA/PLLA films showed lower surface contact angle and faster degradation degree compared with PLLA films. Moreover, the cytotoxicity test of PEDOT-HA/PLLA films showed that neuron-like pheochromocytoma (PC12) cells adhered and spread well on the surface of PEDOT-HA/PLLA films and cell viability denoted by MTT assay had a significant increase. PEDOT-HA/PLLA films modified with laminin (LN) also exhibited an efficiently elongated cell morphology observed by fluorescent microscope and metallographic microscope. Furthermore, PEDOT-HA/PLLA films were subjected to different current intensity to elucidate the effect of electrical stimulation (ES) on neurite outgrowth of PC12 cells. ES (0.5 mA, 2 h) significantly promoted neurite outgrowth with an average value length of 122 ± 5 µm and enhanced the mRNA expression of growth-associated protein (GAP43) and synaptophysin (SYP) in PC12 cells when compared with other ES groups. These results suggest that PEDOT-HA/PLLA film combined with ES are conducive to cell growth and neurite outgrowth, indicating the conductive PEDOT-HA/PLLA film may be an attractive candidate with ES for enhancing nerve regeneration in nerve tissue engineering.

Removal of natural organic matter in a typical south-China source water during enhanced coagulation with IPF-PACl.

Systematic investigation on enhancing removal of natural organic matter (NOM) using inorganic polymer flocculant (IPF), polyaluminum chloride (PACl) and polyacrylamide (PAM) was performed in a typical south-China source water. Enhanced coagulation and applying polymer flocculant-aid were compared through jar tests and pilot tests. Raw water and settled water were characterized and fractionated by resin adsorption. The results show that DOC composes major part of TOC. The DOC distribution keeps relatively stable all around the year with typical high amounts of the hydrophilic matter around 50%. The distribution between HoB, HoA and HoN varies and undergoes fluctuation with the year round. During the summer season, the HoN becomes gradually the major part in hydrophobic parts. PACI with the species being tailor-made shows little pH effect during coagulation. The enhanced coagulation dosage for PACI could be 4.5 mg/L for the typical source water. The highest TOC removal achieved 31%. To be economically, 3 mg/L dose is the optimum dosage. Although hydrophilic fractions of NOM of both treatment strategies are removed about 30%, NOM causing UV254. absorbance were well removed(about 90%). Hydrophobic bases and acids fractions are much more removed under enhanced conditions. The hydrophilic fraction could be better removed using PAM, the polymer coagulant aid.

[Effects of polymer aluminum hydrolysis on phosphorus distribution in coagulation].

Coagulation treatment was conducted by using coagulants of different basicity (ratio of OH(-)/Al); contents,distributions and algal availability of phosphorus in water were studied before and after coagulation. Results show that: phosphorus removals and its distribution in water were markedly different according to the coagulant with different basicity used; Al(a) plays an important role in the coagulation experiment for P removal. The lower the coagulant basicity was, the higher phosphorus removal was achieved; and PACl0 showed the best performance. Dissolved and particulate phosphorus reduced gradually with the increase of the coagulant (PACl0). They were entirely turned into deposit phosphorus when the coagulant dosage was above 10 mg x L(-1). The demand of coagulant for turbidity control was proved to be unequal to that for phosphorus removal. The coagulant dosages of about 3-5 mg x L(-1) achieved the best turbidity removal in the experiment; while much higher dosage was needed to get desired phosphorus removal. The amount of AAP (algal available phosphorus) in the sediments changed according to coagulant (PAC10) dosages. AAP increased with the increase of coagulant dosage when the dosage was less than 5 mg x L(-1), then it decreased with further addition of coagulant above 5 mg x L(-1). It was proved that release of phosphorus in sediments would be controlled effectively by addition of coagulant overdosed compared to the need for turbidity removal, which is important to long-term control of phosphorus. It was indicated that the dosage of coagulant used for phosphorus removal can not use the sole criterion for turbidity removal; the need for total phosphorus removal, sediment release of available phosphorus (such as AAP) and other phosphorus control requirements should be considered; and a larger dosage would be needed.