An interesting evolution of the re-entrant interaction has been observed in an anionic silica nanoparticle (NP)-block copolymer (P85) dispersion due to mutually competing effects of temperature and ...polymer concentration. It has been demonstrated that a rise in the temperature leads to an evolution of attraction in the system, which interestingly diminishes on increasing the polymer concentration. Consequently, the system exhibits a re-entrant transition from repulsive to attractive and back to repulsive at a given temperature but with respect to the increasing polymer concentration, within a selected region of concentration and temperature. The intriguing observations have been elucidated based on the temperature/concentration-dependent modifications in the interactions governing the system, as probed by contrast-variation small-angle neutron scattering. The initial transition from the repulsive to attractive system is attributed to the temperature-driven enhancement in the hydrophobicity of the amphiphilic triblock copolymer (P85) adsorbed on nanoparticles. The strength and range of this attraction are found to be more than van der Waals attraction while relatively less than electrostatic interaction. At higher polymer concentrations, the saturation of polymer adsorption on nanoparticles introduces additional steric repulsion along with electrostatic interaction between their conjugates, effectively reducing the strength of the attraction. However, with a significant increase in temperature (>75 °C), the attraction again dominates the system, which eventually leads to the particle aggregation at all the measured polymer concentrations (>0.1 wt %). Our study provides useful inputs to develop smart NP-polymer composites having capabilities to respond to external stimuli such as temperature/concentration variation.An interesting evolution of the re-entrant interaction has been observed in an anionic silica nanoparticle (NP)-block copolymer (P85) dispersion due to mutually competing effects of temperature and polymer concentration. It has been demonstrated that a rise in the temperature leads to an evolution of attraction in the system, which interestingly diminishes on increasing the polymer concentration. Consequently, the system exhibits a re-entrant transition from repulsive to attractive and back to repulsive at a given temperature but with respect to the increasing polymer concentration, within a selected region of concentration and temperature. The intriguing observations have been elucidated based on the temperature/concentration-dependent modifications in the interactions governing the system, as probed by contrast-variation small-angle neutron scattering. The initial transition from the repulsive to attractive system is attributed to the temperature-driven enhancement in the hydrophobicity of the amphiphilic triblock copolymer (P85) adsorbed on nanoparticles. The strength and range of this attraction are found to be more than van der Waals attraction while relatively less than electrostatic interaction. At higher polymer concentrations, the saturation of polymer adsorption on nanoparticles introduces additional steric repulsion along with electrostatic interaction between their conjugates, effectively reducing the strength of the attraction. However, with a significant increase in temperature (>75 °C), the attraction again dominates the system, which eventually leads to the particle aggregation at all the measured polymer concentrations (>0.1 wt %). Our study provides useful inputs to develop smart NP-polymer composites having capabilities to respond to external stimuli such as temperature/concentration variation.
Herein we describe the H‐bonding‐regulated nanostructure, thermodynamics, and multivalent binding of two bolaamphiphiles NDI‐1 and NDI‐2 consisting of a hydrophobic naphthalene diimide connected to a ...hydrophilic wedge by a H‐bonding group and a glucose moiety on its two arms. NDI‐1 and NDI‐2 differ by the single H‐bonding group, namely, hydrazide or amide, which triggers the formation of vesicles and cylindrical micelles, respectively. Although the extended H‐bonding ensures stacking with head‐to‐head orientation and the formation of an array of the appended glucose moieties in both systems, the adaptive cylindrical structure exhibited superior multivalent binding with concanavalin A (ConA) to that of the vesicle. A control amphiphile lacking a H‐bonding group assembled with a random lateral orientation to produce spherical micelles without any notable multivalent binding.
Bonded with a purpose: Two bolaamphiphiles consisting of a hydrophobic naphthalene diimide unit connected at one end to a hydrophilic wedge by a H‐bonding group (hydrazide or amide) and at the other to a glucose moiety showed distinct H‐bonding‐regulated behavior with the formation of vesicles or cylindrical micelles (see picture). The adaptive cylindrical micelles formed by amide H‐bonding exhibited superior multivalent binding with concanavalin A.
Polyurethane nanocomposites with varying concentration of different fillers are produced through hot melt extrusion by using nanotalc and Cloisite 30B as fillers. The TEM images show good dispersion ...of 30B while moderate agglomeration in nanotalc composite. The result is supported by the respective nanostructures (exfoliated in 30B vs. intercalated in nanotalc composites). A slight decrease in degradation temperature is observed but the nanocomposites are thermally stable upto 300°C. Permeability significantly decreases for nanocomposites. Young's modulus increases with increasing filler concentration while the toughness improvement exhibits a maximum at 4 and 6 wt% of 30B and nanotalc, respectively. Halpin–Tsai model is employed to predict the mechanical properties of the composites. The mechanical, thermal and gas barrier properties are better in 30B as compared to nanotalc nanocomposites, due to greater interaction in 30B nanocomposites evident from the large shift of peak position in UV–vis and FTIR measurements along with its good dispersion.
Enhaced mechanical and gas barrier properties of PU nanocomposites.
pH-dependent growth of CTAB micelles in the presence of p-toluic acid.
•CTAB micelles show structural changes with solubilized additives.•p-Toluic acid, p-toluidine and p-cresol showed pH dependent ...micellar growth.•The dissimilar effects of these additives are explained from pH dependent changes.
In this manuscript we report pH induced micellar transition in aqueous solution of cetyltrimethylammonium bromide (CTAB) in the presence of three weakly polar aromatic additives viz. p-toluic acid, p-cresol and p-toluidine scrutinized by viscosity, nuclear magnetic resonance (NMR), dynamic light scattering (DLS) and small-angle neutron scattering (SANS) measurements. Interaction between these additives and CTAB micelles changes the size and shape of the micelles. Variation in pH alters the charge on the polar group and leads to protonation/deprotonation of acidic/basic group of the additives. Depending upon the pH of solution additives interact with CTAB micelles and accordingly change the solution behavior/aggregation characteristics. Morphological changes of surfactant aggregates as a function of additive concentration and pH were monitored by SANS measurements. NMR studies reveal a pH dependent location of the additive molecules in the micelles.
We report molecular interaction‐driven self‐assembly of supramolecularly engineered amphiphilic macromolecules (SEAM) containing a single supramolecular structure‐directing unit (SSDU) consisting of ...an H‐bonding group connected to a naphthalene diimide chromophore. Two such SEAMs, P1‐50 and P2‐50, having the identical chemical structure and hydrophobic/hydrophilic balance, exhibit distinct self‐assembled structures (polymersome and cylindrical micelle, respectively) due to a difference in the H‐bonding group (hydrazide or amide, respectively) of the single SSDU. When mixed together, P1‐50 and P2‐50 adopted self‐sorted assembly. For either series of polymers, variation in the hydrophobic/hydrophilic balance does not alter the morphology reconfirming that self‐assembly is primarily driven by directional molecular interaction which is capable of overruling the existing norms in packing parameter‐dependent morphology control in an immiscibility‐driven block copolymer assembly.
Amphiphilic block‐copolymers: A directional molecular interaction overrules classical packing parameters and enacts new rules for the self‐assembly of supramolecularly engineered amphiphilic polymer assemblies. The self‐assembly is governed by a distinct H‐bonding motif of a single H‐bonding moiety present in the entire polymer chain.
Display omitted
In-situ inclusion of different nanoclays during synthesis results in different level of dispersion of nanoclays in the polymer matrix depending upon the surface modification of the ...nanoclay. Higher intercalation of the polymer chains within the galleries of organically modified nanoclay results better dispersion as compared to pristine nanoclay. The spectroscopic measurement shows that the extent of interaction between the nanoclay and polymer chains is higher in modified nanoclay nanocomposite which decreases the crystallinity considerably as compared to pristine clay nanocomposite. Interestingly, shape memory behavior measured at physiological temperature (37 °C) improves significantly in presence of organically modified nanoclay while it decreases in presence of unmodified nanoclay in same polyurethane matrix. Complete melting of soft segment along with restricted flipping of hard segment with temperature in presence of extensive interaction in nanocomposite with modified nanoclay helps it to achieve better shape memory behavior against flipping induced stacking of hard segment with temperature along with poor interaction decreases its shape memory behavior in nanocomposite with unmodified nanoclay. Temperature dependent nanostructure reveals the cause of variation in shape memory behavior in presence of organically modified nanoclay. Further, the cell culture studies like cell adhesion, cell viability assay and fluorescence imaging, suggest superior biomaterial of the nanocomposite with modified nanoclay as compared to other composite. Better biodegradable nature of the modified nanocomposite makes it suitable candidate for its potential biomedical applications.
The size-dependent interaction of anionic silica nanoparticles with ionic (anionic and cationic) and nonionic surfactants has been studied using small-angle neutron scattering (SANS). The surfactants ...used are anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethyl ammonium bromide (DTAB), and nonionic decaoxyethylene n-dodecylether (C12E10). The measurements have been carried out for three different sizes of silica nanoparticles (8, 16, and 26 nm) at fixed concentrations (1 wt % each) of nanoparticles and surfactants. It is found that irrespective of the size of the nanoparticles there is no significant interaction evolved between like-charged nanoparticles and the SDS micelles leading to any structural changes. However, the strong attraction of oppositely charged DTAB micelles with silica nanoparticles results in the aggregation of nanoparticles. The number of micelles mediating the nanoparticle aggregation increases with the size of the nanoparticle. The aggregates are characterized by fractal structure where the fractal dimension is found to be constant (D ≈ 2.3) independent of the size of the nanoparticles and consistent with diffusion-limited-aggregation-type fractal morphology in these systems. In the case of nonionic surfactant C12E10, micelles interact with the individual silica nanoparticles. The number of adsorbed micelles per nanoparticle increases drastically whereas the percentage of adsorbed micelles on nanoparticles decreases with the increase in the size of the nanoparticles.
Cellulosic bioethanol is a promising renewable and substitute source of energy. To make the bioconversion of LCB to fuels cost effective and energy efficient, it is essential to reduce the ...recalcitrance of LCB and unravel the process of biomass deconstruction. Present study employed sequential dilute acid-alkali pretreatment of sugarcane bagasse (SCB) for enhancing its bioconversion to ethanol. Box-Behnken and D-optimal designs were used to optimise the process of dilute acid and alkali pretreatments sequentially, resulting in an optimum concentration of 3% (v/v) and 5% (w/v) for H2SO4 and NaOH with solid SCB loadings of 18 and 15% (w/w), respectively, for 30 min at 121 °C. The effectiveness of sequential pretreatment was supported by increased cellulose content (83%), drop in hemicellulose, enhanced delignification and 60% enzymatic hydrolysis of SCB by in-house Trichoderma reesei cellulases at enzyme dose of 20 FPU/g. The favourable multi-length scale ultrastructural changes in SCB induced by pretreatment were confirmed by FT-IR, SEM, EDX, TGA, XRD and small angle neutron scattering (SANS). SANS revealed increase in small pore radii from 11.1 to 18.5 Å, indicating improved biomass porosity after sequential pretreatment. Thus, sequential pretreatment of LCB effectively reduced the recalcitrance and could be more useful in lignocellulosic biorefinery applications.
Display omitted
•83% cellulose after sequential dilute acid-alkali pretreatment of SCB.•Decreased crystallinity and transition to amorphous cellulose after pretreatment.•SANS employed first time to probe structural changes in SCB.•Increased porosity of sequentially pretreated SCB confirmed by SANS.
Small-angle neutron scattering (SANS) and UV–visible spectroscopy studies have been carried out to examine pH-dependent interactions and resultant structures of oppositely charged silica ...nanoparticles and lysozyme protein in aqueous solution. The measurements were carried out at fixed concentration (1 wt %) of three differently sized silica nanoparticles (8, 16, and 26 nm) over a wide concentration range of protein (0–10 wt %) at three different pH values (5, 7, and 9). The adsorption curve as obtained by UV–visible spectroscopy shows exponential behavior of protein adsorption on nanoparticles. The electrostatic interaction enhanced by the decrease in the pH between the nanoparticle and protein (isoelectric point ∼11.4) increases the adsorption coefficient on nanoparticles but decreases the overall amount protein adsorbed whereas the opposite behavior is observed with increasing nanoparticle size. The adsorption of protein leads to the protein-mediated aggregation of nanoparticles. These aggregates are found to be surface fractals at pH 5 and change to mass fractals with increasing pH and/or decreasing nanoparticle size. Two different concentration regimes of interaction of nanoparticles with protein have been observed: (i) unaggregated nanoparticles coexisting with aggregated nanoparticles at low protein concentrations and (ii) free protein coexisting with aggregated nanoparticles at higher protein concentrations. These concentration regimes are found to be strongly dependent on both the pH and nanoparticle size.
The simultaneous presence of Fe3+ and As3+ ions in groundwater (higher ppb or lower ppm level concentrations at circumneutral pH) as well as in acid mine drainages (AMDs)/industrial wastewater (up to ...few thousand ppm concentration at strongly acidic pH) are quite common. Therefore, understanding the chemical interactions prevalent between Fe3+ and As3+ ions in aqueous medium leading to nucleation of ionic clusters/solids, followed by aggregation and growth, is of great environmental significance. In the present work, we attempt to probe the nucleation process of Fe3+-As3+ clusters in solutions of various concentrations and pHs (from AMD to groundwater-like) using a combination of experimental and theoretical techniques. Interestingly, our study reveals nucleation of primary FeAs clusters in nearly all of them independent of concentration or pH. Theoretical studies employed density functional theory (DFT) to predict the primary clusters as stable Fe4As4 units. The surprising resemblance of these clusters with known Fe3+-As3+ minerals at the local level was observed experimentally, which provides an important clue about solid-phase growth from a range of Fe3+-As3+ solutions. Our experimental findings are further supported by a stepwise reaction mechanism established from detailed DFT studies.
