Project description:Three series of alkoxy chain-bearing azobenzene-derived quaternary ammonium iodides with an alkoxy chain at one end, namely N,N-diethanol-6-(4-((4'-alkyloxyphenyl)diazenyl)phenoxy)hexan-1-ammonium iodides, N-ethyl-N-ethanol-6-(4-((4'-alkyloxyphenyl)diazenyl)phenoxy)hexan-1-ammonium iodides and N,N-diethyl-6-(4-((4'-alkyloxyphenyl)diazenyl)phenoxy)hexan-1-ammonium iodides were synthesized and characterized. Their mesomorphic and photoswitching properties were examined via polarising optical microscopy (POM), differential scanning calorimetry (DSC) and UV-vis spectrophotometry. The liquid crystalline tilted schlieren texture of smectic C, non-tilted natural focal conic texture of smectic A and smectic B phases were observed in the N,N-diethanol- and N-ethyl-N-ethanol-bearing ammonium group substituted at the terminal via the alkoxy chain of the azo moiety. In these azo moieties, the equilibrium time for trans-cis isomerization was about 1 min and cis-trans isomerization occurred at around 590 min, which had the highest alkoxy chain and no hydroxyl group on their head group. The absence of a hydroxyl group on the terminal head group resulted in slow thermal back relaxation, whereas the hydroxyl group-bearing head group showed fast thermal back relaxation. These results suggest that the influence of the substituent on the cationic ammonium head group and alkoxy chain length on the photoisomerization of the azo compounds is vital for optical storage devices. Furthermore, the device fabricated using these materials demonstrated that they are excellent candidates for optical image storage applications.
Project description:The elastic modulus of the extracellular matrix is a dynamic property that changes during various biological processes, such as disease progression or wound healing. Most cell culture platforms, however, have traditionally exhibited static properties, making it necessary to replate cells to study the effects of different elastic moduli on cell phenotype. Recently, much progress has been made in the development of substrates with mechanisms for either increasing or decreasing stiffness in situ, but there are fewer examples of substrates that can both stiffen and soften, which may be important for simulating the effects of repeated ECM injury and resolution. In the work presented here, poly(ethylene glycol)-based hydrogels reversibly stiffen and soften with multiple light stimuli via photoisomerization of an azobenzene-containing cross-linker. Upon irradiation with cytocompatible doses of 365 nm light (10 mW/cm(2), 5 min), isomerization to the azobenzene cis configuration leads to a softening of the hydrogel up to 100-200 Pa (shear storage modulus, G'). This change in gel properties is maintained over a time scale of several hours due to the long half-life of the cis isomer. The initial modulus of the gel can be recovered upon irradiation with similar doses of visible light. With applications in mechanobiology in mind, cytocompatibility with a mechanoresponsive primary cell type is demonstrated. Porcine aortic valvular interstitial cells were encapsulated in the developed hydrogels and shown to exhibit high levels of survival, as well as a spread morphology. The developed hydrogels enable a route to the noninvasive control of substrate modulus independent of changes in the chemical composition or network connectivity, allowing for investigations of the effect of dynamic matrix stiffness on adhered cell behavior.
Project description:A series of azobenzene-cholesterol organogel compounds (M 0 -M 12 ) with different spacers were designed and synthesized. The molecular structures were confirmed by (1)H NMR and (13)C NMR spectroscopy. The rapid and reversible photoresponsive properties of the compounds were investigated by UV-vis spectroscopy. Their thermal phase behaviors were studied by DSC. The length of the spacer plays a crucial role in the gelation. Compound M 6 is the only one that can gelate in ethanol, isopropanol and 1-butanol and the reversible gel-sol transitions are also investigated. To obtain visual insight into the microstructure of the gels, the typical structures of the xerogels were studied by SEM. Morphologies of the aggregates change from flower-like, network and rod with different sizes. By using IR and XRD characterization, it is found that intermolecular H-bonding, the solvents and van der Waals interaction are the main contributions to the specific superstructure.
Project description:Azobenzene derivatives are one of the most important molecular switches for biological and material science applications. Although these systems represent a well-known group of compounds, there remains a need to identify the factors influencing their photochemical properties in order to design azobenzene-based technologies in a rational way. In this contribution, we describe the synthesis and characterization of two novel amides (L1 and L2) containing photoresponsive azobenzene units. The photochemical properties of the obtained compounds were investigated in DMSO by UV-Vis spectrophotometry, as well as 1H NMR spectroscopy, and the obtained results were rationalized via Density Functional Theory (DFT) methods. After irradiation with UV light, both amides underwent trans to cis isomerization, yielding 40% and 22% of the cis isomer of L1 and L2 amides, respectively. Quantum yields of this process were determined as 6.19% and 2.79% for L1 and L2, respectively. The reverse reaction (i.e., cis to trans isomerization) could be achieved after thermal or visible light activation. The analysis of the theoretically determined equilibrium structure of the transition-state connecting cis and trans isomers on the reaction path indicated that the trans-cis interconversion is pursued via the flipping of the substituent, rather than its rotation around the N=N bond. The kinetics of thermal back-reaction and the effect of the presence of the selected ions on the half-life of the cis form were also investigated and discussed. In the case of L1, the presence of fluoride ions sped the thermal relaxation up, whereas the half-life time of cis-L2 was extended in the presence of tested ions.
Project description:The unique characteristics of water-based hydroxyethyl sulfone (HES)-vinyl sulfone (VS) dynamic equilibrium are exploited in the design of new reactive coalescing agents (RCAs) for the first time to address VOC (Volatile Organic Compound) emission issues from waterborne coatings. New RCAs were synthesized as HES analogues of widely used commercial coalescing agents (CAs) and characterized. These HES based RCAs are found to be effective towards film formation as evidenced by minimum film formation temperature (MFFT) studies. Equilibration of HES to VS of these RCAs was established and the VS intermediate was isolated and characterized. Detailed studies reveal that HES analogues of RCAs react with amine/hydroxyl containing monomers and latex only during the film formation through VS formation, while HES remains unreactive during storage in water or aqueous basic solution. The current study demonstrates the potential use of HES compounds as RCAs towards environmentally benign waterborne coatings. The reactivity of HES analogues towards latex polymer is found to be promoted during the film formation without use of any other external triggers like heat or light.
Project description:Understanding the spatiotemporal effects of surface topographies and modulated stiffness and anisotropic stresses of hydrogels on cell growth remains a biophysical challenge. Here we introduce the photolithographic patterning or two-photon laser scanning confocal microscopy patterning of a series of o-nitrobenzylphosphate ester nucleic acid-based polyacrylamide hydrogel films generating periodically-spaced circular patterned domains surrounded by continuous hydrogel matrices. The patterning processes lead to guided modulated stiffness differences between the patterned domains and the surrounding hydrogel matrices, and to the selective functionalization of sub-regions of the films with nucleic acid anchoring tethers. HeLa cells are deposited on the circularly-shaped domains functionalized with the MUC-1 aptamers. Initiation of the hybridization chain reaction by nucleic acid tethers associated with the continuous hydrogel matrix results in stress-induced ordered orthogonal shape-changes on the patterned domains, leading to ordered shapes of cell aggregates bound to the patterns.
Project description:Two modified types of hyperbranched polymer were successfully prepared using hyperbranched polyether (HBPE) as a matrix, cis-5-norbornene-endo-2,3-dicarboxylic anhydride (CDA) or o-phthalic anhydride (PA) as a modifier and by grafting an NCO-terminated compound (IPDI-HEA). The modified hyperbranched polymers were incorporated into a typical water-soluble polyacrylate (WPA) as crosslinkers to develop high-performance waterborne UV-curable coatings via electrophoretic deposition (EPD). Although the particle size of the electrophoretic dispersion increased from 43.8 nm to 164 nm, no microphase separation occurred, and the smooth SEM images of the coatings confirmed their uniformity. The rate of photopolymerization (R p) and percentage conversion of the double bonds increased with increasing active unsaturated double bond content, and were partially affected by steric effects. Thermal gravity analysis and tensile tests indicated that the UV-curable EPD coating films exhibited better thermal stability due to their hyperbranched structure, soft and hard segment content and crosslinking density. The coated tin plate could resist chemical corrosion after immersion in NaCl solution. The coatings demonstrated strong adhesion to extremely bent tin plates and outstanding tolerance to knife-scratches and impact. This is a promising method for the design of desirable coatings in the EPD industry.
Project description:The recycling of polyethylene terephthalate (PET) is the most attractive method for PET waste management because it not only decreases the load on landfill space, but also provides opportunities for reducing the use of raw petrochemical products. Therefore, in this investigation, neopentyl glycol is used for alcoholysis of waste PET, and glycolyzed PET product was applied for preparation of the waterborne alkyd resin. Furthermore, the waterborne alkyd-amino baking coatings were prepared from the waterborne alkyd based on glycolyzed waste PET and melamine formaldehyde resin and applied on tinplate. The waterborne alkyd-amino resin films showed excellent adhesion, balanced hardness and flexibility, high gloss and outstanding chemical resistance except for alkali resistance owing to hydrolysis of ester bonds.
Project description:Photoinduced structural changes in peptides can dynamically control the formation and dissociation of supramolecular peptide materials. However, the existence of photoresponsive viral capsids in nature remains unknown. In this study, we constructed an artificial viral capsid possessing a photochromic azobenzene moiety on the peptide backbone. An azobenzene-containing β-annulus peptide derived from the tomato bushy stunt virus was prepared through solid-phase synthesis using Fmoc-3-[(3-aminomethyl)-phenylazo]phenylacetic acid. The azobenzene-containing β-annulus (β-Annulus-Azo) peptide showed a reversible trans/cis isomerization property. The β-annulus-azo peptide self-assembled at 25 μM into capsids with the diameters of 30-50 nm before UV irradiation (trans-form rich), whereas micrometer-sized aggregates were formed after UV irradiation (cis-form rich). The artificial viral capsid possessing azobenzene facilitated the encapsulation of fluorescent-labeled dextrans and their photoinduced release from the capsid.
Project description:Superamphiphobic coatings may significantly change the wettability of a substrate, and so are attractive for applications in aero/marine engineering, biotechnology, and heat transfer. However, the coatings are caught in a double bind when their durability is considered, as they are vulnerable to mechanical abrasion. Meanwhile, the wide use of organic solvents for preparing the coatings generates environmental pollution. Here, we present a waterborne superamphiphobic coating through one-step spraying that repels a wide range of liquids. By tailoring the repellence of the nano-silica to waterborne resin, a network structure is constructed to protect the embedded nano-silica from damage. Thus, the coatings are durable against 725 cycles of friction tester abrasion under a load of 250 g, showing a significant improvement in the mechanical durability by 3-25 times. Moreover, our coating also shows excellent comprehensive durability, including resistance to oil-flow erosion, falling sand impact, chemical attack, thermal treatment, etc. This strategy can be introduced to various waterborne resins, demonstrating its universality, and may offer a new insight to design sustainable superamphiphobic coatings for long-term practical applications.