Locking the Spiro Carbon in Spirobisindane Using Sulfur and Phosphorus to Form "Olympic Ring"-like Molecules.

To improve the rigidity of spirobisindane, it was intramolecularly locked by forming eight-membered rings via sulfur and phosphorus atoms to produce an interlocked polycyclic structure under mild conditions in good yields. By carefully analyzing the crystal structures, we noticed that the angle between the two benzene rings in the locked version is significantly smaller than that of the typical spirobisindane structure. Molecular modeling indicated that locking the spiro center can remarkably enhance the rigidity.

A Versatile 3D and 4D Printing System through Photocontrolled RAFT Polymerization.

Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a valuable tool for synthesizing macromolecules with controlled topologies and diverse chemical functionalities. However, the application of RAFT polymerization to additive-manufacturing processes has been prevented due to the slow polymerization rates of typical systems. In this work, we developed and optimized a rapid visible (green) light mediated RAFT polymerization process and applied it to an open-air 3D printing system. The reaction components are non-toxic, metal free and environmentally friendly, which tailors these systems toward biomaterial fabrication. The inclusion of RAFT agent in the photosensitive resin provided control over the mechanical properties of 3D printed materials and allowed these materials to be post-functionalized after 3D printing. Additionally, photoinduced spatiotemporal control of the network structure provided a one-pass approach to 4D printed materials. This RAFT-mediated 3D and 4D printing process should provide access to a range of new functional and stimuli-responsive materials.

Molecular Weight and Charge Density Effects of Guanidinylated Biodegradable Polycarbonates on Antimicrobial Activity and Selectivity.

Six guanidine functionalized aliphatic biodegradable polycarbonates with varying molecular weights and charge densities were synthesized via postsynthesis modification of alkyne containing polycarbonates using Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry. The concept of passive diluting group was to modify the cationic charge density of the polycarbonate without changing its hydrophilicity. Within the molecular weight range from 8000 to 30000 g mol-1, these guanidine polycarbonates exhibited broad-spectrum biocidal activity with low toxicity to red blood cells (RBCs). The lowest molecular weight homopolymer sample (PG-8k-100) showed the best antimicrobial activity (MIC = 40 µg/mL against Escherichia coli and MIC = 20 µg/mL against Staphylococcus epidermidis) and least RBC toxicity (0.6% hemolysis at MIC). Within the three guanidine charge densities from 20% to 70%, the low to medium dilution samples (PG-8k-7030 and PG-8k-5050) had no obvious loss in antimicrobial activities compared to the nondiluted control sample PG-8k-100. However, upon further dilution, PG-8k-2080 gave the lowest antimicrobial activity.

Preparation of microbial agent immobilized composites for Cr(VI) removal from wastewater.

Because of its extreme toxicity and health risks, hexavalent chromium [Cr(VI)] has been identified as a major environmental contaminant. Bioreduction is considered as one of effective techniques for cleaning up Cr(VI)-contaminated sites, but the remediation efficiency needs to be enhanced. Here, a novel immobilized microbial agent was produced by immobilizing Bacillus cereus ZY-2009 with sodium alginate (SA) using polyvinyl alcohol (PVA) and activated carbon (AC). To evaluate the decrease of Cr(VI) by immobilized bacterial agents, batch tests were conducted with varying immobilization conditions, immobilization carriers, and dosages of medication. The removal of Cr(VI) by the agent prepared by the composite immobilization method was better than that by the adsorption and encapsulation methods. The optimal preparation conditions were the fraction of magnetic PVA was 5.00%, the fraction of SA was 4.00%, the fraction of CaCl2 was 4.00%, and the calcification time was 12 h. The experimental results indicated that PVA/SA/AC agents accelerated the reduction rate of Cr(VI). The removal rate of Cr(VI) by immobilized cells (90.5%) under ideal conditions was substantially higher than that of free cells (11.0%). This novel agent had a large specific surface area and a rich pore structure, accounting for its high reduction rate. The results suggest that the PVA/SA/AC immobilized Bacillus cereus ZY-2009 agent has great potential to remove Cr(VI) from wastewater treatment systems.

Hexavalent chromium removal by a resistant strain Bacillus cereus ZY-2009.

Bioreduction of Cr(VI) to Cr(III) by reducing microbes has attracted increasing concern. Here, Cr(VI) removal capacity of a Cr(VI)-resistant bacterium isolated from activated sludge was investigated. Based on its physio-biochemical attributes and 16S rDNA sequence analysis, the strain was identified as Bacillus cereus ZY-2009. It grew normally in the media containing 10-100 mg/L Cr(VI), indicating its high resistance to Cr(VI). Under the optimal conditions of pH 7.0, inoculation amount 10%, and temperature 30°C, Cr(VI) was effectively removed, with a removal rate of ∼80%. Co-existing Fe3+ and Cu2+ greatly increased Cr(VI) removal, but Cd2+ showed significant inhibition. Cr(VI) was removed mainly via enzyme-mediated bioreduction but not biosorption. Cr(VI) was reduced by different cell fractions (i.e. extracellular secretions, cytoplasm, and cell envelope), implying that Cr(VI) can be reduced both extracellularly and intracellularly. This strain can be used in the bioremediation of Cr(VI)-containing wastewater, with Fe3+ and Cu2+ as stimulators.

Guanidinylated Amphiphilic Polycarbonates with Enhanced Antimicrobial Activity by Extending the Length of the Spacer Arm and Micelle Self-Assembly.

Nine guanidinylated amphiphilic polycarbonates are rationally designed and synthesized. Each polymer has the same biodegradable backbone but different side groups. The influence of the hydrophobic/hydrophilic effect on antimicrobial activities and cytotoxicity is systematically investigated. The results verify that tuning the length of the spacer arm between the cationic guanidine group and the polycarbonate backbone is an efficient design strategy to alter the hydrophobic/hydrophilic balance without changing the cationic charge density. A spacer arm of six methylene units (CH2 )6 shows the best antimicrobial activity (minimum inhibitory concentration, MIC = 40 µg mL-1 against Escherichia coli, MIC = 20 µg mL-1 against Staphylococcus aureus, MIC = 40 µg mL-1 against Candida albicans) with low hemolytic activity (HC50 > 2560 µg mL-1 ). Furthermore, the guanidinylated polycarbonates exhibit the ability to self-assemble and present micelle-like nanostructure due to their intrinsic amphiphilic macromolecular structure. Transmission electron microscopy and dynamic light scattering measurements confirm polymer micelle formation in aqueous solution with sizes ranging from 82 to 288 nm.

Effective Conversion of Amide to Carboxylic Acid on Polymers of Intrinsic Microporosity (PIM-1) with Nitrous Acid.

Carboxylate-functionalised polymers of intrinsic microporosity (C-PIMs) are highly desirable materials for membrane separation applications. The recently reported method to afford C-PIMs was via an extensive base hydrolysis process requiring 360 h. Herein, a novel and effective method to convert PIM-CONH2 to C-PIM using nitrous acid was studied. The chemical structure of C-PIM was characterised by ¹H NMR, 13C NMR, FTIR, elemental analysis, UV-Vis, TGA and TGA-MS. Complete conversion from amide to carboxylic acid groups was confirmed. Decarboxylation of C-PIM was also successfully studied by TGA-MS for the first time, with a loss of m/z 44 amu (CO2) observed at the first degradation stage. TGA also revealed decreased thermal stability of C-PIM relative to PIM-CONH2 under both N2 and air atmosphere. Gel permeation chromatography (GPC) analysis showed continuous molecular weight degradation of C-PIM with extended reaction time. Aromatic nitration was also observed as a side reaction in some cases.

The enhancement of chain rigidity and gas transport performance of polymers of intrinsic microporosity via intramolecular locking of the spiro-carbon.

Here, we present a new strategy to improve the rigidity of through the introduction of 8-membered ring locking into the flexible spiro-carbon pivot point to produce an interlocked polycyclic structure. This locked version of shows simultaneous increases in both permeability and selectivity that place it well above the Robeson upper bound for a number of important gas pairs. Molecular modelling demonstrates that the locked version of is much more rigid.

Light-responsive in situ forming injectable implants for effective drug delivery to the posterior segment of the eye.

INTRODUCTION: Frequent intravitreal injections are currently the preferred treatment method for diseases affecting the posterior segment of the eye. However, these repeated injections have been associated with pain, risk of infection, hemorrhages, retinal detachment and high treatment costs. To overcome these limitations, light-responsive in situ forming injectable implants (ISFIs) may emerge as novel systems providing site-specific controlled drug delivery to the retinal tissues with great accuracy, safety, minimal invasiveness and high cost efficiency. AREA COVERED: Complex ocular barriers, routes for drug delivery, types of injectable implants, ocular application of light and benefits of light-responsive systems are discussed with regards to challenges and strategies employed for effective drug delivery to the posterior segment of the eye. In particular, we have highlighted photoresponsive moieties, photopolymerization mechanisms and different development strategies with their limitations as well as recent advancements in the field. EXPERT OPINION: Biodegradable light-responsive ISFIs are promising drug delivery systems that have shown a high degree of biocompatibility with sustained drug release in a number of applications. However, their use in intravitreal drug delivery is still in the very early stages. Issues related to the biocompatibility of the photoinitiator and the elimination of photo-degraded by-products from the ocular tissues need careful consideration, not only from a chemistry standpoint, but also from a biological perspective to improve the suitability of these systems for clinical applications.

Influence of heat curing on structure and physicochemical properties of phenolic acid loaded proteinaceous electrospun fibers.

Effects of heat treatment on structure and physicochemical properties of zein (Ze) and gallic acid loaded zein (Ze-GA) electrospun fiber mats were investigated. The electrospun fiber mats displayed different surface and physicochemical properties after being heat-cured at 150 °C for 24 h, which were closely related to the initial amount of loaded gallic acid. The gallic acid was released from the Ze-GA fiber mats in a constant manner, but heat curing decreased the rate of release. Heat curing remarkably increased the molecular weight of the Ze and Ze-GA electrospun fiber mats. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis of the fiber mats indicated variations in zein protein secondary structure after heat curing. (13)C solid state NMR (SS-NMR) confirmed the presence of a different chemical environment among the fiber mats. The fabrication of heat-cured zein based electrospun fibers in this study may find applications in the food packaging industry.

Evaluation of gallic acid loaded zein sub-micron electrospun fibre mats as novel active packaging materials.

The applicability of gallic acid loaded zein (Ze-GA) electrospun fibre mats towards potential active food packaging material was evaluated. The surface chemistry of the electrospun fibre mats was determined using X-ray photon spectroscopy (XPS). The electrospun fibre mats showed low water activity and whitish colour. Thermogravimetric analysis (TGA) and Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy revealed the stability of the fibre mats over time. The Ze-GA fibre mats displayed similar rapid release profiles, with Ze-GA 20% exhibiting the fastest release rate in water as compared to the others. Gallic acid diffuses from the electrospun fibres in a Fickian diffusion manner and the data obtained exhibited a better fit to Higuchi model. L929 fibroblast cells were cultured on the electrospun fibres to demonstrate the absence of cytotoxicity. Overall, the Ze-GA fibre mats demonstrated antibacterial activity and properties consistent with those considered desirable for active packaging material in the food industry.

Encapsulation of food grade antioxidant in natural biopolymer by electrospinning technique: a physicochemical study based on zein-gallic acid system.

Gallic acid was successfully incorporated into zein ultra-fine fibres at different loading amount (5%, 10% and 20%) in order to develop an encapsulating technology for functional ingredient delivery using electrospinning. The produced fibres exhibit diameters ranging from 327 to 387 nm. The physical and thermal properties of encapsulated gallic acid were determined by X-ray diffraction (XRD) and differential scanning calorimetry (DSC); and the interaction between gallic acid and zein was attested by attenuated total reflection-Fourier transform infrared (ATR-FTIR). Thermogravimetric analysis (TGA) demonstrated a different thermal stability of the fabricated complex before and after the gallic acid incorporation. Lastly, the 1,1'-diphenyl-2-picrylhydrazyl (DPPH) assay showed that the gallic acid had retained its antioxidant activity after incorporation in zein electrospun fibres. Overall, electrospinning technique had shown promising results as an efficient and effective method for the preparation of sub-micron structured encapsulated functional ingredient that may find uses in food industry.

Effect of mesoscopic fillers on the polymerization induced viscoelastic phase separation at near- and off-critical compositions.

We have investigated the effect of mesoscopic fillers on the polymerization induced viscoelastic phase separation of thermoplastic modified thermosets at near- and off-critical concentrations using optical microscopy, time-resolved light scattering, dynamic mechanical analyses, and rheological instrument. Mesoscopic fillers including sepiolite and nanosized silica showed a significant enhancement effect in viscoelastic phase separation, and resulted in pronounced differences in the phase structures at all concentrations of polyetherimide modified epoxy resins with dynamic asymmetry. For blends near critical concentration, the introduction of fillers led to much finer phase structure with smaller characteristic length scale. At off-critical composition (i.e., blends with low concentration of slow dynamic component), the strong polymer chain entanglement resulted in enwrapped mesoscopic fillers within a slow dynamic phase. The rheological behavior of the blends clearly demonstrated the significant enhancement effect of mesoscopic fillers in the viscoelastic phase separation. The apparent activation energy of polymer chain mobility obtained from dynamic mechanical study of glass transition reflected strong wrapping behavior of polymer chains on mesoscopic fillers, which were consistent with the rheological and light scattering study.

Synthesis and electronic factors in thermal cyclodimerization of functionalized aromatic trifluorovinyl ethers.

A series of 19 p-substituted aromatic trifluorovinyl ether compounds were prepared from versatile intermediate p-Br-C(6)H(4)-O-CF=CF(2) and underwent thermal radical mediated cyclodimerization to new difunctional compounds containing the 1,2-disubstituted perfluorocyclobutyl (PFCB) linkage. The synthetic scope demonstrates the functional group transformation tolerance of the fluorovinyl ether, and the dimers are useful as monomers for traditional step-growth polymerization methods. (19)F NMR spectra confirmed that p-substitution affects the trifluorovinyl ether group chemical shifts. The first kinetic studies and substituent effects on thermal cyclodimerization were performed, and the results indicated that electron-withdrawing groups slow the rate of cyclodimerization. The data were further analyzed using the Hammett equation, and reaction constants (rho) of -0.46 at 120 degrees C and -0.59 at 130 degrees C were calculated. This study presents the first liner free energy relationship reported for the cyclodimerization of aromatic trifluorovinyl ethers to PFCB compounds.