Rheology and microstructure of thermoresponsive composite gels of hematite pseudocubes and Pluronic F127.

Stimuli-responsive materials or smart materials are designed materials whose properties can be changed significantly by applying external stimuli, such as stress, electric or magnetic fields, light, temperature, and pH. We report the linear and nonlinear rheological properties of thermoresponsive composite gels based on submicron-sized hematite pseudocube-shaped particles and a triblock copolymer Pluronic F127 (PF127). These novel composites form hard gels at an elevated temperature of 37 °C. For certain concentrations (<20 w/v. %) of hematite pseudocubes in 17.5 w/v. % of PF127, the gel strength is enhanced and the brittleness of the gels decreases. Higher concentrations (>20 w/v. %) of hematite pseudocubes in PF127 result in weaker and fragile gels. We develop an extensive rheological fingerprint using linear and nonlinear rheological studies. Adsorption of PF127 copolymer molecules on the hematite cube surfaces would further assist the formation of particle clusters along with magnetic interactions to be held effectively in the PF127 micellar network at elevated temperatures. The microscopic structure of these composite gels is visualized through a confocal microscope. Our experiments show that addition of hematite cubes up to 20 w/v. % does not change the rapid thermal gelation of PF127 solutions; hence, the hematite-PF127 composite, which transforms into a hard gel near human body temperature of 37 °C, could be suitable for use in smart drug delivery systems.

Boron-doped carbon quantum dots: a 'turn-off' fluorescent probe for dopamine detection.

Boron-doped carbon quantum dots (size 2.3 nm) were fabricated by a modified hydrothermal carbonization one-pot synthesis protocol using 4-hydroxy phenylboronic acid as the common precursor that provided seed for the formation of carbon quantum dots as well as the dopant. These quantum dots exhibited excellent properties, namely good aqueous dispersion, strong fluorescence emission, good environmental stability, high selectivity and sensitivity towards the neurochemical dopamine even in the absence of any linker, functionalizing agents or enzyme. It is shown that this material can be used as a 'turn-off' fluorescent probe for the detection of even low concentrations of dopamine with a limit of detection (3σ/S) of about 6 µM. The simplicity of the synthesis protocol and the ease of dopamine detection define the novelty of this approach.

Boron Doped Carbon Quantum Dots: Turn-Off Fluorescent Probe for Dopamine Detection.

In this report, Boron-doped carbon quantum dots (BCQD, size = 2.3 nm) were fabricated by modified hydrothermal carbonization method by one-pot synthesis using phenyl boronic acid as the common precursor that provided seed for the formation of carbon quantum dots as well as the dopant. These quantum dots exhibited excellent properties including aqueous dispersibility, strong fluorescence emission, good environmental stability, highselectivity and sensitivity towards the neurochemical, dopamine even in the absence of any linker or functionalizing agents. It is shown that this material can be used as a "turn off" fluorescent probe for the detection of even low concentration of dopamine with a minimum detection limit of ~6 µM. The simplicity of synthesis protocol and the easiness of dopamine detection define the novelty of this approach.

Ubiquity of complex coacervation of DNA and proteins in aqueous solution.

We report complex coacervation between a primarily hydrophobic protein, elastin, and a strong polyanion DNA (2 kbp) in aqueous and salty solutions at room temperature, 25 °C. The associative interaction at fixed elastin and varying DNA concentration, thereby maintaining a mixing ratio of r = [DNA] : [elastin] = 0.0027 to 0.093, was probed. What distinguishes this study from protein-DNA coacervation reported earlier is that the protein used here was mostly a hydrophobic polyampholyte with low linear charge density, and its complementary polyelectrolyte, DNA, concentration was chosen to be extremely small (1-35 ppm). The interaction profile was found to be strongly hierarchical in the mixing ratio, defined by three distinct regions: (i) Region I (r < 0.02) was defined as the onset of primary binding leading to condensation of DNA; (ii) Region II (0.02 < r < 0.08) indicated secondary binding which led to the formation of fully charge neutralized complexes signaling the onset of coacervation; and (iii) Region III (0.08 < r < 0.12) revealed growth of insoluble complexes of large size facilitating liquid-solid phase separation. The degree of complex coacervation was suppressed in the presence of a monovalent salt implying that screened Coulomb interactions governed the binding. Small angle neutron scattering data attributed an amorphous structure to the coacervates. The elastin-DNA system belongs to a rare class of interacting biopolymers where very weak electrostatic interactions may drive coacervation, thereby implying that coacervation between DNA and proteins may be ubiquitous.

Multifunctional, fluorescent DNA-derived carbon dots for biomedical applications: bioimaging, luminescent DNA hydrogels, and dopamine detection.

Here, we describe the synthesis of 2-3 nm, hydrophilic, blue fluorescence-emitting carbon dots (C-Dots, made using a DNA precursor) by the hydrothermal route from the gelling concentration of 2% (w/v) DNA. These dots exhibited highly efficient internalization in pathogenic fungal cells, negligible cytotoxicity, good PL stability, and high biocompatibility, thus demonstrating their potential as nanotrackers in microbial studies. Bioimaging was performed using Candida albicans as the representative for microbial pathogens. The novelty of these dots is that they formed fluorescent nanocomposite hydrogels with the same DNA much below the gelation concentration (1% w/v) and the tunable gels possessed strength between 20 and 80 Pa with the corresponding gelation temperature Tgel between 40 to 50 °C. The network density and gelation free energy data supported the superior crosslinking ability of these dots. The as-prepared hydrogels can replace the existing toxic quantum dot-based hydrogels for drug delivery. We also demonstrated the use of a DNA hydrogel-fabricated working electrode (DNA-C-Dot/ITO electrode) for the biosensing of dopamine. Our electrochemical biosensor had a detection limit of 5 × 10-3 mM for dopamine. These multifunctional, fluorescent C-Dots and hydrogel after suitable conjugation or loading with molecules and drugs hold promising potential for further exploitation in bioimaging, targeted drug delivery, wound healing, and biosensing applications.

pH responsive doxorubucin loaded zein nanoparticle crosslinked pectin hydrogel as effective site-specific anticancer substrates.

Herein, we report pH-responsive hydrogels of hierarchically self-assembled protein (zein, in the form of its nanoparticles of size 80-120 nm) and polysaccharide (pectin), where gelation occurred below pH 3 in the absence of crosslinkers, which we used for encapsulation and release of anticancer drug, Doxorubicin (DOX) in the cell nucleus. These nanoparticles, spherical in shape, in addition to helping in the formation of gel network also encapsulate the drug and pectin layer adsorbed on the surface of these nanoparticle allows for the drying, redispersion and enhanced swelling. A monovalent salt-dependent study performed in the concentration range of 1-100 mM clearly showed the associative interaction between the zein nanoparticles and pectin chains were hydrophobic in nature. FTIR results confirmed the loading of the drug inside the nanoparticles. Melting profile studies of these gels revealed that encapsulation of drug did not change the thermo-physical properties. Doxorubicin drug loaded hydrogels exhibited superior cytotoxicity towards cervical cancer cell lines by inducing intracellular-antioxidative stress-based apoptosis. Confocal microscopy revealed that the hydrogels required quite less time of 4 h to completely penetrate the cells assisted by the charge specific electrostatic interaction between the negatively charged HeLa cells and positively charged crosslinks. The data, further revealed that these pH specific hydrogels were suitable for release of the drug in cell nucleus is assisted by the acidic environment of cellular organelles, and hence have a potential in cancer therapy with minimal collateral damage to healthy cells.

Fluorescent complex coacervates of agar and in situ formed zein nanoparticles: Role of electrostatic forces.

Herein, the complex coacervation between in situ formed spherical fluorescent zein nanoparticles and polyanion agar as function of mixing ratio (R=[Agar]/[Zein]) was investigated. This interaction yielded two distinguishable regions (at pH 5.4): Region I (R < 0.2), where fully charge neutralized soluble complexes with protein denaturation was noticed, and Region II (R > 0.2), where overcharged complexes were formed, with R = 0.2 defining the optimum binding. Small angle neutron scattering studies demonstrated that in the low-q region, nanoparticles formed the crosslink junctions and in the persistence regime of high-q region, the data captured the cross-sectional radius ( = 3.5 nm) for agar-zein complexes. The coacervates became more viscoelastic in salt-free samples because both the low frequency storage modulus and crosslink density were found to decrease with mixing ratio. Systematic decrease in storage modulus with ionic strength (0-0.01 M) implied screened Coulomb interaction was responsible for the observed coacervation. Further, we seek to find universality in complex coacervation of zein nanoparticle with biopolymers, and polysaccharides in particular.

Hierarchical self-assembly, spongy architecture, liquid crystalline behaviour and phase diagram of Laponite nanoplatelets in alcohol-water binary solvents.

Hydrophobicity and solvation of different charged species are among the various key factors that regulate the self-assembly of colloids, and macromolecules in their suspensions. In this paper, we demonstrate a method to tune the interaction potential and the resulting phase behaviour and microstructure of the states that form by using a combination of Laponite nanoplatelets and alcohols in water. This allows us to exquisitely control the self-assembly process of Laponite nanoplatelets. A new class of soft materials, called nanoclay-organogels, is studied systematically for their aging behaviour, microscopic structure and mechanical properties. Real space imaging techniques depicted spongy architecture with nano and micron size pores inside the gel matrix indicating the hierarchical self-assembly of the nanoplatelets in the aqueous solutions of polar organics. We have extensively examined the dispersion stability, aggregation, gelation and liquid crystalline behaviour of Laponite nanoplatelets in different alcohol (methanol, ethanol, 1-proponaol and ethylene glycol, and glycerol)-water binary solvents, thereby proposing a generalized description of nanoclay in alcoholic solutions, which is poorly probed and marginally understood in the literature. A phase diagram of Laponite® in alcohol solutions is proposed, which clearly demarcates regions of isotropic sol, unstable sol, isotropic gel, nematic/birefringent gel, glass, flocculated sedimentation and liquid crystalline structures.

Effect of organic and inorganic salt environment on the complex coacervation of in situ formed protein nanoparticles and DNA.

Complex coacervation was noticed between in situ formed protein (a primarily hydrophobic Zein protein with pI = 6.2) nanoparticles (size 80-120 nm) and ds-DNA (a high charge density polyanion), in the ionic liquid (IL) solutions of 1-ethyl-3-methyl imidazolium chloride [C2mim][Cl], and 1-octyl-3-methyl imidazolium chloride [C8mim][Cl], in the studied ionic strength range of I = 10-4 to 6 × 10-1 M, which was extended to strong monovalent 1:1 electrolyte (NaCl) to explore the commonality between the organic and inorganic salt (ionic) environment on coacervation. The salt dependent coacervation profile was monitored from the measured turbidity of the interacting solution, and zeta potential, (ζ) and apparent hydrodynamic radius (Rh) of interpolymer complexes, which depicted the following three discernible interaction regimes common to all the salts: (i) Region-I: I = 0.0001-0.01 M, primary binding, (ii) Region-II, I = 0.01-0.1 M, secondary binding, and (iii) Region-III, I = 0.1-0.6 M, saturation binding. The free-energy and the network density calculations favored preferential coacervation in [C2mim][Cl] samples. Nonetheless, commonality in the overall ionic strength dependent coacervation profiles could still be observed.

Mixing ratio dependent complex coacervation versus bicontinuous gelation of pectin with in situ formed zein nanoparticles.

We report on the competitive phenomenon of complex coacervation versus bicontinuous gelation between pectin (P, a polyanionic carbohydrate, [P] = 0.01-2% (w/v)) and zein nanoparticles (Z, a hydrophobic protein and a weak polyampholyte, [Z] = 0.1 and 0.5% (w/v), in an ethanolic solution of effective concentration 4 and 27% (v/v)), which was studied below (pH ≈ 4), and above (pH ≈ 7.4) the pI (≈ 6.2) of zein at room temperature, 25 °C. The uniqueness of this study arises from the interaction protocol used, where the pectin used was in the extended polyelectrolyte (persistence length ≈ 10 nm) conformation while zein was used as a charged globular nanoparticle (size ≈ 80-120 nm) that was formed in situ. Their mixing ratio, r = [P] : [Z] (w/w), was varied from 0.02 to 4.0 (for [Z] = 0.5% (w/v)), and from 0.1 to 7.5 (for [Z] = 0.1% (w/v)) in the ionic strength range 10-4 to 10-2 M NaCl. Zeta potential data revealed that at pH ≈ 4, the complementary binding condition, r = 1 : 1 (equivalent to 1 : 5 molecule/nanoparticle) demarcated the coacervate from the gel region. The measured rigidity (G0, low frequency storage modulus) of these materials revealed the following: for r < 1, (low pectin content samples, coacervate region) the material had lower values of Gcoac0, whereas for r > 1, an excess of pectin facilitated gelation with Ggel0 ≫ Gcoac0. Above pI, surface patch binding caused associative interactions and complex coacervation though both biopolymers had similar net charge. The network density was used as a descriptor to distinguish between the coacervate and gel samples. Their microstructures were probed by small angle neutron scattering (SANS), and viscoelastic properties by rheology. Simple modeling shows that formation of the interpolymer complex was favored in higher protein containing samples. Mixing ratio dependent selective coacervation (a kinetic process) and bicontinuous gelation (a thermodynamic process) are rarely seen to coexist in biopolymer interactions.

Bandgap Tunable AgInS based Quantum Dots for High Contrast Cell Imaging with Enhanced Photodynamic and Antifungal Applications.

Herein, we report a facile microwave-assisted synthesis of cadmium-free water-soluble silver indium sulfide (AgInS2 or AIS) and AgInS@ZnS (or AIS@ZnS) core-shell quantum dots (QDs) using glutathione (GSH) as stabilizer. The core and core-shell nanocrystals exhibit tunable bandgap ranging of 2.3-3.1 and 2.4-3.5 eV, mean particle size of 2.5 and 3.25 nm, quantum yield of 26% and 49%, and fluorescence lifetimes of 326 and 438 ns, respectively. The core-shell QDs exhibit color-tunable emission in the visible region (500 to 600 nm), where the tunability was achieved by varying the molar ratio of Ag:In in the precursors. In vitro evaluation of antifungal activity of these water/ buffer stable QDs against the fungal pathogen, Candida albicans demonstrated that these were not toxic to the fungal cells upto a concentration of 100 µg/ml for 16 hours of incubation. Confocal imaging and spectrofluorometric studies showed enhanced fluorescence inside the microbial cells suggesting that AIS@ZnS particles had the capability to easily penetrate the cells. The increased generation of reactive oxygen species was evaluated for the core-shell QDs (photosensitizers) by using 9, 10-anthracenediyl-bis(methylene)dimalonic acid (ABMDMA) as singlet oxygen (1O2) scavenger molecule. These QDs have the potential for use as high contrast cell imaging, photodynamic and antifungal agents.

In-situ Observation of Hierarchical Self-Assembly Driven by Bicontinuous Gelation in Mixed Nanodisc Dispersions.

The search for new functional soft materials with precise and reconfigurable structures at the nano and meso-scale is a major challenge as well as objective of the current science. Patchy colloids of different shapes and functionalities are considered important new building blocks of a bottom-up approach towards rational design of new soft materials largely governed by anisotropic interactions. Herein, we investigate the self-assembly, growth of hierarchical microstructures and aging dynamics of 2D nano-platelets of two different aspect ratios (Laponite ~25 and Montmorillonite ~250) which form gels with different porosity that is achieved by tuning their mixing ratios. Qualitative in situ real-space studies are carried out, including fluorescent confocal microscopy imaging of the bicontinuous gelation process or final states, which provides dynamic visualization of the self-organization. The bicontinuous gels exhibit a foam-like morphology having pores of a few micrometers in size that can be tuned by varying the mixing ratio of nanoplatelets. It is shown that this new class of clay gels has unique and tunable physical properties that will find potential applications in the development of low cost lithium ion batteries, nanocomposites and nuclear waste management.

Antifungal efficacy of Au@ carbon dots nanoconjugates against opportunistic fungal pathogen, Candida albicans.

In the current study, we have investigated the toxicological effect of a novel hydrophilic nanoconjugate gold@carbon dot (Au@CD) and carbon dots (CDs) on the opportunistic fungal pathogen, Candida albicans. A homogenous experimental analysis was conducted for determining the toxicity of Au@CDs nanoconjugates of five different sizes ranging from 22 ±â€¯2 to 35 ±â€¯3 nm prepared using the carbon dots of mean hydrodynamic radius 12 ±â€¯1 nm. The smallest size of nanoconjugate was synthesized using 0.3 mg ml-1 HAuCl4 precursor. Our study for the first time, conclusively establishes the size-dependent toxicity effect of these characterized nanoconjugates against the abovementioned fungal pathogen. The MIC80 value of smaller sized Au@CDs nanoconjugates, S1-S3 samples were 250, 500 and 500 µg ml-1, respectively, while nanoconjugates of Rh diameter greater than 30 nm (S4 and S5 samples) did not show any toxicity. The results thus demonstrate that alteration in composition (carbon vs Au@CDs) exhibits a profound effect on the susceptibility of Candida albicans cells. While a size-dependent toxicity was observed for the nanoconjugates, CDs were found to be quite toxic owing to their small size which facilitated their entry into the cells and challenged the biocompatibility of carbon allotropes.

Carbon dots-modified chitosan based electrochemical biosensing platform for detection of vitamin D.

Here in, a carbon dots (CDs)-modified chitosan (CH) based biosensing platform was fabricated for vitamin D2 detection. Carbon dots were synthesized through microwave pyrolysis method, and characterized with transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and UV/VIS spectroscopy. Chitosan (1%) solution was prepared in acetic acid (1%) solution and followed by the addition of CDs to prepare the carbon dots-chitosan (CD-CH) composite. A thin film of CD-CH composite was prepared onto ITO glass substrate (CD-CH/ITO) by drop casting method. Surface of the composite film was characterized by atomic force microscopy, static contact angle measurement and cyclic voltammetry. CD-CH/ITO surface was further modified with immobilization of vitamin D2 antibody (Ab-VD2) and bovine serum albumin (BSA) to prepare BSA/Ab-VD2/CD-CH/ITO bioelectrode. Electrochemical response of the bioelectrode towards vitamin D2 antigen (Ag-VD2) was carried out by differential pulse voltammetry. The biosensing electrode showed linearity within the range 10-50 ng mL-1 of Ag-VD2 concentration. The sensitivity was found to be 0.2 µA ng-1 mL cm-2, LOD was 1.35 ng mL-1, and the biosensor had a shelf-life of about 25 days.

Eco-friendly synthesis of CuInS2 and CuInS2@ZnS quantum dots and their effect on enzyme activity of lysozyme.

We report on the green and facile aqueous microwave synthesis of glutathione (GSH) stabilized luminescent CuInS2 (CIS, size = 2.9 nm) and CuInS2@ZnS core-shell (CIS@ZnS, size = 3.5 nm) quantum dots (QDs). The core-shell nanostructures exhibited excellent photo- and water/buffer stability, a long photoluminescence (PL) lifetime (463 ns) and high PL quantum yield (PLQY = 26%). We have evaluated the comparative enzyme kinetics of these hydrophilic QDs by interacting them with the model enzyme lysozyme, which was probed by static and synchronous fluorescence spectroscopy. The quantification of the QD-lysozyme binding isotherm, exchange rate, and critical flocculation concentration was carried out. The core-shell QDs exhibited higher binding with lysozyme yielding a binding constant of K = 5.04 × 109 L mol-1 compared to the core-only structures (K = 6.16 × 107 L mol-1), and the main cause of binding was identified as being due to hydrophobic forces. In addition to the enzyme activity being dose dependent, it was also found that core-shell structures caused an enhancement in activity. Since binary QDs like CdSe also show a change in the lysozyme enzyme activity, therefore, a clear differential between binary and ternary QDs was required to be established which clearly revealed the relevance of surface chemistry on the QD-lysozyme interaction.

Complex coacervation in charge complementary biopolymers: Electrostatic versus surface patch binding.

In this review, a number of systems are described to demonstrate the effect of polyelectrolyte chain stiffness (persistence length) on the coacervation phenomena, after we briefly review the field. We consider two specific types of complexation/coacervation: in the first type, DNA is used as a fixed substrate binding to flexible polyions such as gelatin A, bovine serum albumin and chitosan (large persistence length polyelectrolyte binding to low persistence length biopolymer), and in the second case, different substrates such as gelatin A, bovine serum albumin, and chitosan were made to bind to a polyion gelatin B (low persistence length substrate binding to comparable persistence length polyion). Polyelectrolyte chain flexibility was found to have remarkable effect on the polyelectrolyte-protein complex coacervation. The competitive interplay of electrostatic versus surface patch binding (SPB) leading to associative interaction followed by complex coacervation between these biopolymers is elucidated. We modelled the SPB interaction in terms of linear combination of attractive and repulsive Coulombic forces with respect to the solution ionic strength. The aforesaid interactions were established via a universal phase diagram, considering the persistence length of polyion as the sole independent variable.

Solvent hydrophobicity induced complex coacervation of dsDNA and in situ formed zein nanoparticles.

Zein, a predominantly hydrophobic protein, was sustained as a stable dispersion in ethanol-water (80 : 20, % (v/v)) binary solvent at room temperature (25 °C). Addition of aqueous dsDNA solution (1% (w/v)) to the above dispersion prepared with the protein concentration of Czein = 0.01-0.5% (w/v) caused a concomitant change in ethanol content from 14-35% (v/v), which in turn generated zein nanoparticles in situ of size 80-120 nm increasing with water content. The subsequent associative interaction between DNA (polyanion; 2000 bps) and the positively charged zein nanoparticles, (at pH = 4) was driven by Coulombic forces, and by the solvent hydrophobicity due to the ethanol content of the binary solvent. Experimentally, two interesting regions of interaction were observed from turbidity, zeta potential, particle sizing, and viscosity data: (i) for Czein < 0.2% (w/v), zein nanoparticles of size 80 nm bind to dsDNA (primary complex) causing its condensation (apparent hydrodynamic size decreased from ≈2100 to 560 nm), and (ii) for 0.2% < Czein < 0.5% (w/v) larger nanoparticles (>80 nm) were selectively bound to primary complexes to form partially charge neutralized interpolymer soluble complexes (secondary complexes), followed by complex coacervation. During this process, there was depletion of water in the vicinity of the nucleic acid, which was replaced by hydration provided by the ethanol-water binary solvent. Equilibrium coacervate samples were probed for their microstructure by small angle neutron scattering, and for their viscoelastic properties by rheology. The interplay of solvent hydrophobicity, electrostatic interaction, and zein nanoparticle size dependent charge neutralization had a commensurate effect on this hitherto unexplored coacervation phenomenon.

Folic acid supramolecular ionogels.

Herein, we report on folic acid (FA, a low molecular weight gelator) thermoreversible supramolecular organo (in 1 : 1 (v/v) water-DMSO binary solvent), and ionogels made in 1-ethyl-3-methyl imidazolium chloride, [C2mim][Cl], and 1-octyl-3-methyl imidazolium chloride, [C8mim][Cl], solutions with 0.1 ≤ [IL] ≤ 5% (w/v). The self-assembled fibrils of folic acid were largely formed due to secondary forces, such as π-π stacking, H-bonding, and hydrophobic interactions above a gelator concentration of 0.2% (w/v) at room temperature, 20 °C. Fragile gels (FGs) having a low frequency storage modulus G0 ≈ 4-6 Pa were formed when 0.2 ≤ [FA] ≤ 0.5% (w/v) in the binary solvent, and at higher gelator concentration (0.5 ≤ [FA] ≤ 2.5% (w/v)) formation of strong gels (SGs) with a G0 value of 140 Pa-5 kPa was noticed. In the IL environment, for a given gelator concentration of [FA] = 1% (w/v), SG formation (with G0 ≈ 2-5 kPa) was noticed when 0.1 ≤ [IL] ≤ 0.5% (w/v), whereas very strong gels (VSGs) with remarkably high gel strengths were formed with G0 ≈ 11-15 kPa. Gelation temperature Tgel could be varied from 45 to 75 °C by varying the FA concentration in the binary solvent, whereas the ionogels exhibited an almost 10 °C rise in gelation temperature. The information obtained from the relative network density νr (ratio of network density in iono- to organo gel), differential free-energy and enthalpy of gelation, ΔGW-IL and ΔHW-IL (difference in free-energy and enthalpy of organo to ionogel), implied that [C2mim][Cl] ionogels had enhanced homogeneity, and higher crosslink density and gel strength. A 3-D plot of Tgel and G0versus gelator concentration clearly defines a phase diagram that describes the contour of the gelation domains of this biologically important gelator.

Hydrophobic hydration and anomalous diffusion of elastin in an ethanolic solution.

Elastin is an important structural protein that confers elasticity to tissues. It is widely used in the biosynthesis of human elastic tissues and exhibits interesting properties. This study reports an insight into the unusual dispersion and anomalous diffusion of elastin in an ethanolic solution. Due to its complex hydrophobic structure, its dispersibility was found to be sensitive towards the hydrophobicity of the solvent. Electrophoresis measurements (zeta-potential data) revealed that its net polarity changed from an anionic to a cationic state with the decreasing solvent hydrophobicity (ethanol content in the solvent). An interesting transition temperature of ∼297 K was observed above which the hydrophobic interactions among the protein molecules became dominant. Double-layer repulsion between protein molecules competes with attractive hydrophobic interactions and causes molecular self-organization. A DLVO-based theoretical model showed that hydrophobic interactions were facilitated by a binary solvent (ethanol-water), and the repulsive double layer screening provided sufficient energy to overcome the interactions between hydrophobic domains in the protein molecule and allow the self-assembly to occur.

Self-healing gelatin ionogels.

We demonstrate room temperature (20°C) self-healing, and substantial recovery (68-96%) of gel rigidity of gelatin, a polypeptide, ionogels (made in 1-ethyl-3-methylimidazolium chloride ionic liquid (IL) solutions via thermal treatment, IL≤5% (w/v)) after they were cut using a surgical blade. The recovery process did not require any stimuli, and the complete healing under ambient condition required about 10h.The self-healing owed its origin to the reformation of network structures via imidazolium ion mediated charge quenching of deprotonated residues, and hydrophobic interaction between neighbouring alkyl tails of IL molecules. The rate of healing determined from the growth of rigidity modulus was 20±5 mPa/s independent of ionic liquid content of the gel. This was true regardless of the fact that ionogels containing more IL had a lower gel modulus due to propensity of hydrophobic linkages, but these were agile enough to recover their network structures to a higher degree during the healing process. These features indicate that the gelatin ionogel being biocompatibile, and biodegradable holds great potential for applications in the field of biomedical engineering.