Search

A multiresponsive organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) showed a decrease of fluorescence intensity, decrease in mechanical strength and a change in gel morphology on irradiation with a wavelength of 365 nm. This is attributed to the E-Z isomerization across the C=N bond of I as evidenced from (1)H NMR spectroscopy.

Polyethylene glycol (PEG) is incorporated to improve the mechanical properties of N-fluorenylmethoxycarbonyl-l-tryptophan (FT) hydrogel producing the hybrid (FTP) gels designated as FTP1, FTP2.5, etc. having PEG concentrations of 0.05 and 0.125% (w/v), respectively. Both the FT and FTP1 gels exhibit fibrillar network morphology; the fibers of the FTP1 gel are thinner than those of the FT gel. FTP gels exhibit a magnificent improvement in mechanical properties, and the storage and complex moduli increase with a maximum of ∼2800% for the FTP2.5 gel. Creep recovery experiment exhibits a maximum strain recovery of 90% for the FTP1 gel. The thixotropic property is observed for both FT and FTP gels and the rate of recovery increases with increase of PEG concentration; the latter acts as a molecular adhesive to the gel fibers bringing back the network structure easily. Gelation of FT causes a 5-fold increase of fluorescence intensity due to molecular aggregation, and with increase of FT concentration the ratio of fluorescence intensities at 470 and 395 nm increases. Exploiting the thixotropic property of FT and FTP hybrid gels, doxorubicin (DOX) is successfully encapsulated, and tunable release of DOX using appropriate amount of PEG in the gel matrix under physiological conditions is observed.

Polyaniline (PANI)-zinc sulphide (ZnS) nanocomposites (PAZs) are synthesized by polymerizing aniline in the presence of acetic acid with different concentrations of ZnS nanoparticles (NPs). FESEM and TEM images indicate the nanotube morphology of PANI and ZnS NPs remain adhered to the nanotube surface, but at higher ZnS concentration the nanotube morphology is lost. UV-vis spectra indicate PANI is in the doped state and the doping increases with an increase in ZnS concentration. Fluorescence intensity passes through a minimum with ZnS content and the dc-conductivity of the composites gradually increases with an increase in ZnS NP concentration. The I-V plot of PAZ composites indicates that the photocurrent is higher than that of the dark current at each voltage, and the device exhibits reversible turning "on" and "off" by switching the white light illumination "on" and "off". Dye-sensitized solar cells fabricated with PAZ composites display a reasonably higher power conversion efficiency (η = 3.38%) than pure ZnS NPs. An attempt is made to shed light on the operating mechanism of the DSSC from the impedance data using a Cole-Cole plot by drawing an equivalent circuit illustrating the different electronic and ionic transport processes within the cell.

An equimolar mixture of riboflavin-5′-phosphate sodium salt (RP) and adenine (AD) dissolved in a phosphate buffer (pH 4.0, 1.0% w/v) produces a red coloured transparent thixotropic hydrogel at 30 °C. The gelation of the RPAD system occurs in the pH range of 2–5. FTIR spectra and WAXS patterns indicate self-assembly via H-bonding between the >C=O group of RP and the amino/imino group of AD followed by supramolecular organization through a π-stacking process producing a fibrillar network structure. FESEM images clearly indicate that the nanofibres are produced from the intertwining of helical fibrils. The dynamic frequency sweep experiment of the supramolecular gel at a constant strain of 1% exhibits a wide linear viscoelastic region and a considerably higher G′ value (460 Pa) than that of G′′ (21 Pa) confirming the gel nature of the RPAD system. The hydrogel shows high stiffness (G′/G′′ = 3.3), a high yield stress (σ*) (79.5 Pa) and a moderate critical strain (γ = 17.5%). Time sweep experiments at both low (0.1%) and high strain (100%) indicate the thixotropic property of the gel. The RPAD hydrogel shows non-Newtonian viscosity in the shear rate region (0.1–158 s(−1)) and after that there is a sudden fall of viscosity. The gel melting point obtained by the falling ball method is 6° higher than that obtained by the DSC method probably due to the presence of the thixotropic property of the gel. The UV-vis spectra indicate a red shift of the π–π* transition band of RP in the RPAD xerogel. On excitation of the RPAD hydrogel at 373 nm it shows twelve times enhancement of emission intensity with a 7 nm red shift of the emission peak. This has been attributed to the enhancement of lifetime from 2.2 ns in RP to 3.4 ns in the RPAD hydrogel. With increase of temperature, the fluorescence intensity of the RPAD hydrogel at first increases till 40 °C, then decreases up to 55 °C and it again increases after 60 °C.

A facile approach of nanojacketing DNA in intact conformation is evolved by the in situ polymerization of o-methoxyaniline (OMA) at 30 °C using HAuCl4 as an oxidant and DNA as a soft template. It concomitantly produces poly(o-methoxyaniline) (POMA) and a Au nanojacket encapsulating the double stranded DNA (ds-DNA). The POMA chains remain adhered to the Au nanojacket, facilitating the dissolution of nanojacketed DNA (DNA-Au-POMA) in organic solvent without affecting its conformation. Digestion of the nanojacketed system with saturated iodine solution dejackets the ds-DNA with retention of its conformation, leaving the POMA nanotube. The nanojacketing and dejacketing phenomena are established by transmission electron microscopy (TEM), UV-vis spectroscopy, and CD spectroscopy, and the nanostructure is further characterized by FTIR, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The impedance study of the DNA-Au-POMA sample suggests the Cole-Cole plots at both the impedance and modulus planes and the values of capacitance and electron-transfer resistance of the material (R(et)) are calculated to be 13.74 pF and 388 kΩ, respectively. The presence of a single Debye peak in both the impedance and modulus vs frequency plots suggests an isotropic nature of the system, and the frequency dependent ac-conductivity suggests the presence of short-range translational and reorientational (localized) hopping of charge carriers at lower and higher frequency region.

Three new bicomponent hydrogels of riboflavin (R) with salicylic acid (S), dihydroxybenzoic acid (B) and acetoguanamine (D) in 1:1 molar ratio have been reported. FTIR and UV-vis spectra suggest formation of H-bonded complexes in 1:1 molar ratio of the components. The network consists of tape, bar and helical tubes for RB11, RS11 and RD11 systems, respectively. Reversible first order phase transition and invariant storage modulus (G') with angular frequency (ω) characterise the systems as forming thermoreversible hydrogels. The RD11 gel has the highest gel melting temperature and highest critical strain compared to other gels. WAXS study indicates different crystal structures for different gels. NMR spectra reveals higher shielding of protons in RD11 gel suggesting better π-stacking compared to RS11 and RB11 gels. RD11 gel shows two-fold enhancement of photoluminescence (PL) intensity with a substantial red shift of emission peak but RB11 and RS11 gels show PL-quenching. The gels exhibit a small decrease in lifetime and the PL property is very much temperature and pH dependent. So the complementary molecules have a pronounced effect on morphology, structure, stability and optical property of riboflavin gels.

Lumichrome (L) and melamine (M) produce thermoreversible hydrogels in LM31 and LM11 compositions, but LM13 composition does not produce hydrogel (the numbers indicate the respective molar ratio of the components). The formation of thermoreversible gels is confirmed from morphology, DSC, and rheological experiments where LM13 system does not meet the required characteristics of thermoreversible gels. FTIR spectra suggest that H-bonding between L and M produces the supramolecular complex, and (1)H NMR spectra suggest that pi-stacking of the complex produce fibrillar network structure entrapping a large amount of water producing the hydrogels. The nonplanar structure of LM13 complex probably causes difficulty in pi-stacking, prohibiting the gel formation. The UV-vis spectra show a blue shift of the pi-pi* transition band (354 nm) indicating H-aggregate formation but the pi-pi* band coupled with n-pi* transition (386 nm) shows a constant red shift by 7 nm, indicating independency of pi-stacking on the n-pi* transition in the different LM systems. The PL intensities of LM11 and LM31 gels become more quenched than the intensity of pure L due to formation of nonfluorescent complex (static quenching) in the gels. In the LM13 sol the degree of quenching is less than that of the gels because of absence of energy transfer through the junction points of gels. The increased lifetime values of LM gels compared to that of pure L is also indicative of H-aggregate formation. The PL intensity increases linearly with increase of temperature due to thinning of the fibers decreasing the exciton energy transfer. The emission peak shows a red shift with rise in temperature, indicating H- to J-aggregate transformation, and at the melting temperature it shows a sharp decrease. With both increase and decrease of pH from the neutral pH 7, the gels exhibit higher PL intensity because of sol formation.

Three nanobiocomposites (PRAg31, PRAg11, and PRAg13; the numbers indicate the weight ratios of poly(o-methoxyaniline) (POMA) and ribonucleic acid (RNA), respectively), produced from the same amount of POMA (P) and silver nitrate (AgNO(3)) with differing proportions of RNA (R) are prepared by aging the aqueous solutions of the mixture for 3 weeks at 30 degrees C. The scanning and transmission electron microscopy (SEM and TEM) indicate Ag nanoparticle formation on the hybrid fiber surface and in the PRAg31 system the hybrid fibrils become coated with metallic Ag, the phenomenon being termed as "nanojacketting". The circular dichroism (CD) spectra indicate a small distortion of RNA conformation from A helix toward B helix. FTIR and UV-vis spectra suggest that POMA (emeraldine base, EB) being doped by Ag(+) become oxidized to its pernigraniline base (PB) form and reduce Ag(+) to metallic Ag. The Ag nanoparticles thus produced become stabilized on the fibril surface by co-ordination through nitrogen atoms of POMA (PB) chains. The much slower red shift of pi band to polaron band transition peak in PRAg31 than that of the other two nanobiocomposites is indicative of difficulty in conformational transitions of POMA chain in the "nanojacketted" hybrid fibrils. The dc-conductivity values of the nanobiocomposites are two orders higher than that of the pure POMA-RNA hybrids. The PRAg31 system exhibits rectification property in the I-V characteristic curves and a probable explanation based on the feasibility of p-n junction formation arising from the transfer of lone pair of electrons of nitrogen of POMA (p-type) to the Ag nanoparticles (n-type) has been offered.

Nanostructured poly(3-thiophene methyl acetate) (PTMA) within the poly(vinylidene fluoride) (PVDF) matrix is achieved by reactive blending technique under melt-cooled condition. The nanoparticles are almost spherical showing a minimum size with 5% (w/w) PTMA concentration (PTMA5), and they become agglomerated at > or = 25% (w/w) PTMA concentration. Different phase separation mechanisms are used to explain the above variation of nanoparticle size. The lower size nanophase in the PTMA5 blend is attributed to spinodal decomposition, while the larger size nanophases are produced from binodal decomposition. The TGA study indicates increasing thermal stability of PVDF in the nanoblends. DSC study shows increasing melting and crystallization temperature of the nanoblends; the former is due to the attractive forces of PTMA nanostructure, and the latter is for the nucleating effect of nanophase PTMA. The long distance, lamellar distance, and amorphous overlayer distance decrease to different extents. The pi-pi* transition band of UV-vis spectra shows a red shift with increasing PTMA concentration, but the photoluminescence spectra of the nanoblends show a blue shift. The former is attributed to intrachain aggregation of PTMA, while the latter is caused from "static excimer" formation at the ground state. PTMA1 and PTMA3 show approximately 8 times increase in PL intensity except PTMA5 where interconnectivity between the nanodomains makes the nonradiative decay similar to bulk PTMA. The temperature variation of conductivity indicates a conformational transition of PTMA chain with increasing temperature facilitating better charge transport. The I-V characteristic curves are really interesting; the nanoblends show a negative hysterisis, but PTMA5 shows a memory effect attributed to the electrical bistability originated from the interconnected nanophases arising from spinodal decomposition.

An interesting interfacial redox method is developed for the preparation of Au nanoparticles of various shapes in organic medium using Au seeds in aqueous medium without using phase-transfer reagent. The conversion, stabilization, and the transfer of gold nanoparticles to the organic phase is accomplished using the reducing and solubility properties of poly(o-methoxy aniline) in chloroform. The preparatory method is simple, and the Au nanoparticles are free from excess oxidant and external stabilizer. The characterizations of the metal nanoparticles are made using transmission electron microscopy, UV-vis spectra, electron diffraction and energy-dispersive X-ray techniques. Au nanoparticles of various shapes, for example, hexagonal, pentagonal, triangular, rod-shaped, etc. are produced together. A mechanism of the formation of differently shaped nanoparticles is proposed from catalytic reduction of Au(3+) ion by POMA on the Au seed surface followed by the growth of nanoparticles from the exposed Miller planes of seed surfaces.

A novel nano-biocomposite of silver and poly(o-methoxy aniline) (POMA)/DNA hybrid has been prepared by adding DNA solution to an aqueous solution of POMA (emeraldine base, EB) and AgNO(3) mixture. The mixture was aged for 10 days and was freeze-dried to form the hybrid nanocomposite (weight fraction of DNA = 0.75). FESEM pictures show a fibrillar network morphology of the biomolecular hybrid with silver nanoparticles on its surface. The TEM picture also corroborates silver nanoparticle formation in the biomolecular hybrid, and the denser population of nanoparticles in the TEM micrograph as compared to that in the SEM micrograph indicates that the nanoparticles are present inside the fibrils in greater proportion. The dc conductivity value of the hybrid indicates that POMA (EB) is doped by silver ion and the doped POMA form complexes with DNA through electrostatic interaction of the radical cation of POMA (emeraldine salt form, ES) and the DNA anion. During the doping process and Ag nanoparticle formation, a fluctuation of the pi band to polaron band transition peak occurs together with a complementary fluctuation of the polaron band to pi* band transition peak. After 53 h of aging, the former shows a slow but continuous red shift with aging time. This has been attributed to the slow uncoiling of POMA on the DNA surface. The conformation and crystal structure of DNA remain intact during the nano-biocomposite formation. The dc conductivity value of the nano-biocomposite is almost the same as that of the pure POMA-DNA hybrid at the same composition, but the I-V characteristic curve of the nano-biocomposite is somewhat different showing an insulating region on low applied voltage. At higher applied voltage, it shows a semiconducting property characterizing the large band gap semiconducting behavior of the nano-biocomposite.

In situ Ag nanoparticles are produced on reduction of Ag+ with N,N-dimethylformamide in the presence of poly(vinylidene fluoride) (PVF2). The plasmon band transition is monitored with time in the reaction mixture for three sets of experiments by UV-vis spectroscopy. The plasmon band absorbance increases sigmoidally with log(time). Analysis of the data with the Avrami equation yields an exponent n value between 1.5 and 2.0, indicating two-dimensional nucleation with linear or diffusion controlled growth. The TEM study of the polymer nanocomposites (PNC) indicates both spherical and rodlike morphology for PNC0.5 and PNC2.5 samples, whereas the PNC11 sample has spherical and agglomerated structures (the numerical number associated with PNC indicates percentage (w/w) of Ag in the nanocomposite). The WAXS and FTIR studies indicate the formation of piezoelectric beta-polymorphic PVF2 in the nanocomposites. The DSC study indicates some increase of the melting point and enthalpy of fusion of PVF2 in the nanocomposite, although with increase in Ag nanoparticle concentration the increase is smaller. The crystallization temperatures of PNCs also increased, indicating nucleating effect of Ag nanoparticles in the composite. In the TGA curves, the PNCs exhibit a three-step degradation process. The degradation temperatures of PNCs are lower than that of PVF2. The storage modulus data indicate a significant reinforcement of the mechanical property in the PNCs where also the reinforcement effect decreases with increasing nanoparticle concentration. Both the loss modulus and tan delta plots indicate two peaks; the lower temperature peak has been attributed for glass transition temperature, whereas the higher one has been attributed to a similar type relaxation process for the crystalline-amorphous interface. The increase in the glass transition is marginal for the PNCs, but the increase of later transition temperature is somewhat higher. The FTIR study shows that the dipolar interaction of the >CF2 dipole with the surface charges of Ag nanoparticle stabilizes the nanoparticle in the nanocomposite.

The DNA-poly(o-methoxyaniline) (POMA) hybrid is prepared by mixing aqueous solutions of POMA [emeraldine salt (ES), doping level [Cl]/[N] = 0.52] and sodium salt of DNA (Na-DNA) and is then freeze-dried after 4 days. Three different compositions (WDNA = 0.25, 0.5, and 0.75, WDNA is the weight fraction of DNA) of the hybrids are prepared. The SEM pictures show a gradation in morphology; for example, for WDNA = 0.75, fibrils are present but, at lower DNA concentration, a fibrillar network structure of the hybrid is observed. The circular dichroism (CD) spectra of the hybrid solutions indicate unchanged DNA conformation and WAXS patterns indicate intact crystal structure of DNA in the hybrid. The UV-vis spectra suggest no denaturation of DNA during the blending process. The UV-vis spectra of the hybrids in aqueous medium show a gradual red shift of the pi band to polaron band transition with time. The plots of these wavelengths with time are sigmoidal, indicating the autocatalytic nature of the process. With an increase in the temperature, the rate of the red shift of the above peak is faster. Arrhenius analysis of the rate (1/tau700 where tau700 is the time required to reach the absorption maximum at the wavelength 700 nm) yields straight lines for the three hybrid compositions with activation energy values of 13-15 kcal/mol. These values are almost equal to the activation energy values of conformational transition of other polymers, supporting the red shift in UV-vis spectra occurs from conformational transition. DNA offers a surface where POMA gets adsorbed and the stable conformational transition resulting in the uncoiling of the POMA chain occurs through repulsive interaction among bound radical cations of POMA (ES) on the DNA surface. The conductivity of the hybrids is on the order of 10(-6) S/cm, and the I-V characteristic curves indicate the semiconducting nature of the hybrids.

Poly(3-hexyl thiophene) (P3HT) organically modified montmorillonite (om-MMT) polymer nanocomposites (PNCs) are prepared in the melt-cooled state. Hierarchical structures up to third order, namely, side chain mesomorph formation followed by the interchain lamellar structure of P3HT and finally its intercalation within the clay tactoids are observed. The structures are supported by transmission electron microscopy (TEM) and wide-angle X-ray scattering (WAXS) experiments. The TGA curves show two-stage degradation corresponding to those of the side chain and main chain of P3HT, and both temperatures decrease with an increase in clay concentration in the PNCs. The melting points of PNCs have increased by 2-3 degrees C higher than that of P3HT. The glass-transition temperature (Tg) and beta-transition temperature (Tbeta), measured by DMA, increase with an increase in clay concentration. The storage modulus (G) of PNCs has also increased more dramatically than that of P3HT. The UV-vis spectra of the PNCs show a blue shift in the pi-pi* absorption peak of the conjugated chain, but the photoluminescence spectra showed a red shift with an increase in the clay concentration. The quantum yield of the photoluminescence process also increases in the melt-cooled PNCs, and this is in sharp contrast to that of solvent cast PNCs where photoluminescence quenching was observed. Fibrillar network structure of the solvent cast PNCs promotes energy transfer of the charge carriers, but its absence in the melt-cooled films inhibits such energy transfer, increasing the quantum yield. The room-temperature dc conductivity of the PNCs decreased by an order compared to that of P3HT in both the doped and undoped states. The I-V characteristic curve shows semiconducting behavior, and it slowly transforms into insulator with increasing clay concentration.

The dc conductivity of poly(3-alkyl thiophenes) (P3ATs) and their cocrystals are measured in the temperature range of -130 to 150 degrees C. Both solvent-cast films and the melt-cooled films are used. The former exhibit a sharp increase followed by a decrease in conductivity, whereas the latter show only a sigmoidal increase in conductivity with temperature. The sigmoidal increase of the melt-cooled samples is dependent on the regioregularity and alkyl chain length of the samples and is explained from the solid-state transformation of the interdigited type-II crystal to a noninterdigited type-I crystal. The type-I crystal itself has lower conductivity than type-II crystals, and the samples exhibit a blue shift in UV-vis absorption spectra with an increase in temperature. So the sigmoidal increase of conductivity is attributed to the increase in carrier mobility with temperature in the type-I crystals. The X-ray and DSC results suggest that during the transformation of type-II to type-I crystals with increasing temperature, localized crystallites of smaller dimensions separated by narrower amorphous portions are produced throughout the whole matrix. But in the type-II polymorph, the crystallites are large with a wider gap in between. The sigmoidal increase is attributed to the easier hopping of the charge carrier among the localized crystallites of the type-I crystal with increasing temperature. In the cocrystals, the smaller sigmoidal increase with increasing irregular sample concentration is valid for a lower concentration of such localized crystallites. The same is true for cocrystals with longer alkyl chain lengths. The interfibrillar contribution of conductivity through the network junctions together with the carrier hopping between the localized crystallites might be a possible reason for the metallic-type behavior of solvent-cast samples after a certain temperature. The melt-cooled films do not exhibit metallic-type behavior because of the absence of a fibrillar network morphology.

The equilibrium cocrystal formation of poly(3-alkyl thiophene) (P3AT) blends has been studied by isothermal cocrystallization in a differential scanning calorimeter (DSC-7). The equilibrium melting points (T(m)0) of the cocrystals are measured using the Hoffman-Weeks extrapolation procedure. The equilibrium phase diagrams are of three different types: (a) concave upward, (b) linear, and (c) linear with phase separation at higher content of lower melting component. The phase diagram nature depends on the regioregularity difference and also on the difference in the number of carbon atoms in the pendent alkyl group of the components. The origin of biphasic nature of type "c" phase diagram has been explored from the glass transition temperature (Tg) measurement using a dynamic mechanical analyzer. The biphasic compositions show two glass transition temperatures (Tg) as well as two beta transition temperatures (T beta). The T(g)s of phase-separated regions correspond to almost the component values but the T(beta)s correspond to that of a lower (T beta) component value, and the other is higher than that of the higher (T beta) component value. Possible reasons are discussed from the interchain lamella thickness in the P3AT blends and molecular modeling using molecular mechanics program.