Efficient Photocatalytic Degradation of Methylene Blue Dye from Aqueous Solution with Cerium Oxide Nanoparticles and Graphene Oxide-Doped Polyacrylamide.

A cerium oxide nanoparticles (CeO2-NPs)/graphene oxide (GO)/polyacrylamide (PAM) ternary composite was synthesized through free-radical polymerization of acrylamide in the presence of CeO2 nanoparticles and GO in an aqueous system. The synthesized composite material was characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy techniques and applied for the photocatalytic degradation of methylene blue (MB) dye from an aqueous solution. Tauc's model for direct transition was used to model for the optical band gap. The key operating parameters such as the amounts of CeO2-NPs and GO, pH, initial MB concentration, type of light irradiation, and contact time have been optimized to achieve the highest MB degradation percentage. The photocatalysis process was pH-dependent, and the optimum pH value was found to be 12.0. Under UV-A light, 90% dye degradation occurred in 90 min. The degradation of MB was also specified in terms of total organic carbon (TOC) and chemical oxygen demand (COD). Free-radical capture experiments were also performed to determine the role of radical species during the photocatalytic oxidation process. The photocatalytic process showed that the equilibrium data is in good agreement with the Langmuir-Hinshelwood kinetic model. A rate constant of 0.0259 min-1 was obtained. The hydrogel was also tested to assess its reusability, which is an important key factor in practical wastewater treatment. The photocatalytic activity only decreased to 75% after nine uses.

2D Materials (WS2, MoS2, MoSe2) Enhanced Polyacrylamide Gels for Multifunctional Applications.

Multifunctional polymer composite gels have attracted attention because of their high thermal stability, conductivity, mechanical properties, and fast optical response. To enable the simultaneous incorporation of all these different functions into composite gels, the best doping material alternatives are two-dimensional (2D) materials, especially transition metal dichalcogenides (TMD), which have been used in so many applications recently, such as energy storage units, opto-electronic devices and catalysis. They have the capacity to regulate optical, electronic and mechanical properties of basic molecular hydrogels when incorporated into them. In this study, 2D materials (WS2, MoS2 and MoSe2)-doped polyacrylamide (PAAm) gels were prepared via the free radical crosslinking copolymerization technique at room temperature. The gelation process and amount of the gels were investigated depending on the optical properties and band gap energies. Band gap energies of composite gels containing different amounts of TMD were calculated and found to be in the range of 2.48-2.84 eV, which is the characteristic band gap energy range of promising semiconductors. Our results revealed that the microgel growth mechanism and gel point of PAAm composite incorporated with 2D materials can be significantly tailored by the amount of 2D materials. Furthermore, tunable band gap energies of these composite gels are crucial for many applications such as biosensors, cartilage repair, drug delivery, tissue regeneration, wound dressing. Therefore, our study will contribute to the understanding of the correlation between the optical and electronic properties of such composite gels and will help to increase the usage areas so as to obtain multifunctional composite gels.

Surfactant and metal ion effects on the mechanical properties of alginate hydrogels.

This paper addresses the controlled variation of the mechanical properties of alginate gel beads by changing the alginate concentration or by adding different surfactants or cross-linking cations. Alginate beads containing nonionic Brij 35 or anionic sodium dodecyl sulfate (SDS) surfactants were prepared with two different types of cations (Ca2+, Ba2+) as crosslinkers. Compression measurements were performed to investigate the effect of the surfactant and cation types and their concentrations on the Young's modulus of alginate beads. The Young's modulus was determined by using Hertz theory. For all types of alginate gel beads the Young's modulus showed an increasing value for increasing alginate contents. Addition of the anionic surfactant SDS increases the Young's modulus of the alginate beads while the addition of non-ionic surfactant Brij 35 leads to a decrease in Young's modulus. This opposite behavior is related to the contrary effect of both surfactants on the charge of the alginate beads. When Ba2+ ions were used as crosslinker cation, the Young's modulus of the beads with the surfactant SDS was found to be approximately two times higher than the modulus of beads with the surfactant Brij 35. An ion specific effect was found for the crosslinking ability of divalent cations.

Structural analysis of peptide fragments following the hydrolysis of bovine serum albumin by trypsin and chymotrypsin.

Peptide bond hydrolysis of bovine serum albumin (BSA) by chymotrypsin and trypsin was investigated by employing time-resolved fluorescence spectroscopy. As a fluorescent cross-linking reagent, N-(1-pyrenyl) maleimide (PM) was attached to BSA, through all free amine groups of arginine, lysine, and/or single free thiol (Cys34). Time-resolved fluorescence spectroscopy was used to monitor fluorescence decays analyzed by exponential series method to obtain the changes in lifetime distributions. After the exposure of synthesized protein substrate PM-BSA to chymotrypsin and trypsin, it is observed that each protease produced a distinct change in the lifetime distribution profile, which was attributed to distinct chemical environments created by short peptide fragments in each hydrolysate. The persistence of excimer emission at longer lifetime regions for chymotrypsin, as opposed to trypsin, suggested the presence of small-scale hydrophobic clusters that might prevent some excimers from being completely quenched. It is most likely that the formation of these clusters is due to hydrophobic end groups of peptide fragments in chymotrypsin hydrolysate. A similar hydrophobic shield was not suggested for trypsin hydrolysis, as the end groups of peptide fragments would be either arginine or lysine. Overall, in case the target protein's 3D structure is known, the structural analysis of possible excimer formation presented here can be used as a tool to explain the differences in activity between two proteases, i.e. the peak's intensity and location in the profile. Furthermore, this structural evaluation might be helpful in obtaining the optimum experimental conditions in order to generate the highest amount of PM-BSA complexes.

The modifier effects of chymotrypsin and trypsin enzymes on fluorescence lifetime distribution of "N-(1-pyrenyl)maleimide-bovine serum albumin" complex.

Chymotrypsin and trypsin are the well known proteolytic enzymes, both of which are synthesized in the pancreas as their precursors - the inactive forms; chymotrypsinogen and trypsinogen - and then are released into the duodenum to cut proteins into smaller peptides. In this paper, the effects of activities of chymotrypsin and trypsin enzymes on fluorescence lifetime distributions of the substrat bovine serum albumin (BSA) modified with N-(1-pyrenyl)maleimide (PM) were examined. In the labeling study of BSA with PM, it is aimed to attach PM to the single free thiol (Cys34) and to all the free amine groups in accessible positions in order to produce excimers of pyrene planes of the possible highest amount to form the lifetime distributions in the widest range, that may show specifically distinguishing changes resulting from the activities of the proteases. The time resolved spectrofluorometer was used to monitor fluorescence decays, which were analyzed by using the exponential series method (ESM) to obtain the changes of lifetime distributions. After the exposure of the synthesized substrat PM-BSA to the enzymes, the fluorescence lifetime distributions exhibited different structures which were attributed to the different activities of the proteases.

Kinetic models for the dynamical behavior of polyacrylamide (PAAm)-κ-carrageenan (κC) composite gels.

A fluorescence method was employed for studying the drying and swelling of PAAm-κC composite gels, which were formed from acrylamide (AAm) and N, N'- methylenebisacrylamide (BIS) with various κ-carrageenan (κC) contents by free radical crosslinking copolymerization in water. Composite gels were prepared at 80 °C with pyranine (Py) as a fluorescence probe. Scattered light, I sc, and fluorescence emission intensities, I em, were monitored during drying and swelling of these gels. The fluorescence intensity of pyranine increased and decreased as drying and swelling time are increased, respectively, for all gel samples. The Stern-Volmer equation combined with moving boundary and Li-Tanaka models were used to explain the behavior of I em during drying and swelling processes respectively. It is found that the desorption coefficient D d decreased as κC contents were increased for a given temperature during drying. However, the cooperative diffusion coefficient, D s presented exactly the opposite case. Conventional gravimetrical and volumetric experiments were also carried out during drying and swelling of PAAm-κC composite gels. It was observed that D d and D s values measured with the fluorescence method were found to be much larger than they were measured with the conventional methods.

Group behaviour in physical, chemical and biological systems.

Groups exhibit properties that either are not perceived to exist, or perhaps cannot exist, at the individual level. Such 'emergent' properties depend on how individuals interact, both among themselves and with their surroundings. The world of everyday objects consists of material entities. These are, ultimately, groups of elementary particles that organize themselves into atoms and molecules, occupy space, and so on. It turns out that an explanation of even the most commonplace features of this world requires relativistic quantum field theory and the fact that Planck's constant is discrete, not zero. Groups of molecules in solution, in particular polymers ('sols'), can form viscous clusters that behave like elastic solids ('gels'). Sol-gel transitions are examples of cooperative phenomena. Their occurrence is explained by modelling the statistics of inter-unit interactions: the likelihood of either state varies sharply as a critical parameter crosses a threshold value. Group behaviour among cells or organisms is often heritable and therefore can evolve. This permits an additional, typically biological, explanation for it in terms of reproductive advantage, whether of the individual or of the group. There is no general agreement on the appropriate explanatory framework for understanding group-level phenomena in biology.

Cation effect on slow release from alginate beads: a fluorescence study.

In this study, spherical alginate beads containing pyranine (P y ) as a fluorescence probe were prepared by ionotropic gelation of a sodium alginate solution. The steady state fluorescence technique was used to study pyranine release from the alginate beads crosslinked with calcium, barium and aluminum ions, respectively. The slow release of P y was observed with the time drive mode of the spectrophotometer at 512 nm. Fluorescence emission intensity (I p ) from P y was monitored during the release process, and the encapsulation efficiency (EE) of pyranine from the alginate beads was calculated. The Fickian Diffusion model was used to measure the release coefficients, D sl . It was seen that the slow release coefficients of pyranine from the alginate beads crosslinked with Ca(2+), Ba(2+), and Al(3+) ions increased in the following order: D sl (Al(3+))> D sl (Ca(2+))> D sl (Ba(2+)). In contrast, the initial amount of pyranine and EE into the beads showed the reverse behavior.

Oxygen diffusion into multiwalled carbon nanotube doped polystrene latex films using fluorescence technique.

This study examines the oxygen diffusion into polystyrene (PS) latex/multiwalled carbon nanotube (MWNT) nanocomposite films (PS/MWNT) consisting of various amounts of MWNT via steady state fluorescence technique (SSF). PS/MWNT films were prepared from the mixture of MWNT and pyrene (P)-labeled PS latexes at various compositions at room temperature. These films were then annealed at 170 °C above glass transition (Tg) temperature of PS. Fluorescence quenching measurements were performed for each film separately to evaluate the effect of MWNT content on oxygen diffusion. The Stern-Volmer equation for fluorescence quenching is combined with Fick's law for diffusion to derive the mathematical expressions. Diffusion coefficients (D) were produced and found to be increased from 1.1 × 10(-12) to 41 × 10(-12) cm(2)s(-1) with increasing MWNT content. This increase was explained via the existence of large amounts of pores in composite films which facilitate oxygen penetration into the structure.

Sorption and desorption of PVA-pyrene chains in and out of agarose Gel.

In situ steady-state fluorescence (SSF) measurement technique was applied to investigation of pyrene labeled Poly(vinyl alcohol) (PVA-Py) molecules diffusion in and out of agarose gels. Gel samples with four different concentration of agarose were prepared. PVA-Py was synthesized by "click" chemistry method and dissolved in water to use in diffusion experiments. The results were analyzed by using Fickian type diffusion model, and it was found that sorption and desorption processes of PVA-Py molecules in and out of agarose gel have two distinct regions for short and long diffusion times. Sorption and desorption coefficients were measured and it was seen that the diffusion rates were much larger at short times and at lower agarose concentrations.

Thermal phase transitions of agarose in various compositions: a fluorescence study.

The effect of agarose content on thermal phase transitions of the agarose gels was investigated by using Steady State Fluorescence (SSF) method. Scattered light, I(sc) and fluorescence intensity, I(fl) were monitored against temperature during heating and cooling processes to investigate phase transitions. Two regions were observed during the heating and cooling processes. At the high temperature region, double helix to coil (h-c) transition took place. However, during the cooling process coil to double helix (c-h) transitions occurred at low temperature region. Transition energies were determined using the Arrhenius treatment, and found to be strongly correlated with the agarose content in the gel system. Transition temperatures were determined from the derivative of the sigmoidal transition paths and found to be increased by increasing agarose content in both cases.

Drying of polyacrylamide composite gels formed with various kappa- carrageenan content.

Drying of polyacrylamide (PAAm)-κ-carrageenan (κC) composite gels were monitored by using steady-state fluorescence technique. Disc shaped gels were formed from acrylamide (AAm) and N, N'- methylenebisacrylamide(Bis) with various κ- carrageenan (κC) contents by free radical crosslinking copolymerization in water. Pyranine (P) was doped as a fluorescence probe, and scattered light, I (sc), and fluorescence intensities, I, were monitored during drying of these gels. It is observed that fluorescence intensity of pyranine increased as drying time is increased for all samples. The increase in I was modeled using Stern- Volmer equation and diffusion with moving boundary. It is found that desorption coefficient, D decreased as κC contents were increased. Supporting gravimetrical and volumetric experiments were also carried out during drying of PAAm- κC composite gels.

The role of pyranine in characterization of PAAm-κC composites by using fluorescence technique.

Polyacrylamide (PAAm) doped by κ-carrageenan (κC) gels were prepared with various amounts of κC varying in the range between 0 wt.% and 3 wt.%. Steady-state fluorescence (SSF) technique was employed for studying sol-gel transition and swelling of PAAm-κC composite gels which were prepared by free-radical crosslinking copolymerization. Pyranine was introduced as a fluorescence probe. Pyranine molecules start to bind to acrylamide polymer chains upon the initiation of the polymerization, thus the spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allow one to monitor the sol-gel transition and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the gel point, t ( c ) for PAAm-κC composite gels showed that the gel fraction exponent ß obeyed the percolation result for low κC (<2.0 wt. %) however classical results were produced at higher κC (>2.0 wt.%). On the other hand, fluorescence intensity of pyranine was measured during in situ swelling process at various amounts of κC and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li-Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D.

Electrical and optical percolations of polystyrene latex-multiwalled carbon nanotube composites.

Electrical conductivity and optical transmittance properties of polystyrene (PS)-multiwalled carbon nanotube (MWCNT) composite films were investigated. Composite films were prepared by mixing of various mass fractions of MWCNT in PS-water dispersions. After water evaporates, powder composite films were annealed at 175 degrees C above the glass transition of PS for 20 min. Photon transmission and two point probe resistivity techniques were employed to determine the variations of the optical and the electrical properties of composites. Transmitted light intensity, I(tr) and surface resistivity, R(s) were monitored as a function of MWCNT mass fraction (M). It was observed that, both the surface resistivity and the optical transparency were decreased by increasing the amount of MWCNT added to the polymeric system. Conductivity and optical results were interpreted according to the classical and site percolation theory, respectively. The electrical (sigma) and the optical (op) percolation threshold values and critical exponents were calculated as M(sigma)=1.8 wt.%, M(op)=0-0.13 wt.% and beta(sigma)=2.25, beta(op)=0.32, respectively.

Monitoring small molecule diffusion into hydrogels at various temperatures by fluorescence technique.

Steady state fluorescence technique was used to study small molecule diffusion into polyacrylamide (PAAm) gels at various temperatures. Pyranine (P(y)), dissolved in water was introduced as a probe and fluorescence emission (I(p)) from P(y) was monitored during diffusion. Scattered light intensities, I(sc) from PAAm gel was also monitored to observe structural variations during diffusion process. Increase in I(p) intensity was attributed to P(y) diffusion into PAAm gel. On the other hand decrease in I(sc) intensity was interpreted as the variation of the spatial heterogeneities in the system. Li-Tanaka and Fickian models were used to quantify the swelling and diffusion experiments and diffusion coefficients were produced in both cases. Related activation energies were also calculated from the corresponding physical processes.

Universal behaviour of gel formation from acrylamide-carrageenan mixture around the gel point: a fluorescence study.

The steady state fluorescence (SSF) technique was used to study the sol-gel transition, for the solution free radical crosslinking copolymerization of acrylamide (AAm) with various carrageenan content. N, N'- methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) are used as crosslinker and an initiator, respectively. Pyranine (8-hydroxypyrene-1, 3,6-trisulfonic acid, trisodium salt, HPTS) was added as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to acrylamide polymer chains upon the initiation of the polymerization; thus, the spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allows one to monitor the sol-gel transition, without disturbing the system mechanically, and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the critical point show that the gel fraction exponent beta obeyed the percolation result for low carrageenan concentrations (< 2.0%) however classical results were produced at higher carrageenan concentration (> 2.0%).

Vapor-induced film formation from low-Tg particles for different solvent compositions.

The photon transmission method was used to study latex film formation from poly(vinyl acetate) (PVAc) particles induced by two different solvents. Films with the same latex content were prepared from PVAc particles and exposed to vapor of ethanol-water and acetone-water mixtures in various compositions. Transmitted photon intensities, Itr, from these films increased with increasing vapor exposure time. The increase in Itr is attributed to the increase in crossing density at the polymer-polymer junction. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, nu, of the reptating polymer chain during film formation induced by solvent vapor. It was observed that the produced nu values increase as the solvent content is increased for both solvents. Abilities of both solvents to form films were interpreted with the solubility parameters of the solvents and the PVAc.

Film formation from pure and mixed latices; transient fluorescence study.

A fast transient fluorescence technique was used to study latex film formation induced by organic solvent vapor. Mixtures of pyrene (P)- and naphthalene (N)-labeled and/or pure naphthalene-labeled latex films were prepared separately from poly(methyl methacrylate) (PMMA) particles. Then these pure and mixed latex films were exposed to vapor of various chloroform-heptane mixtures in seven different experiments. In both films, fluorescence lifetimes from N were monitored during vapor-induced film formation. It was observed that N lifetimes decreased as the vapor exposure time is increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in N lifetimes. A Prager-Tirrell model was employed to obtain back-and-forth frequencies, nu, of reptating PMMA chains during latex film formation induced by solvent vapor. In both pure and mixed latex films, nu values were found to be correlated with the chloroform content in the vapor mixture. It was observed that polymer interdiffusion obeyed a t1/2 law during film formation.

Photon transmission study on conformational ordering of iota-carrageenan in CaCl2 solution.

Coil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in CaCl(2) solution upon cooling were studied using photon transmission technique. Photon transmission intensity, I(tr) was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (T(ch) and T(hd)) and activation energies (DeltaE(ch) and DeltaE(hd)). An extra dimer-to-dimer (d-d) transition was also observed during cooling at low temperature region. However, upon heating dimers disappear to double helices by making dimer-to-double helix (d-h) transition. Further heating resulted double helix-to-coil (h-c) transition at high temperature region. T(dh) and T(ch) temperatures and DeltaE(dh) and DeltaE(hc) activation energies were also determined. It was observed that T(hc) and T(ch) temperatures and DeltaE(dh) and DeltaE(hd) activation energies do not effected by carrageenan content. However, T(hd), T(dh) and T(dd) temperatures and DeltaE(ch) and DeltaE(hc) activation energies were found to be strongly correlated to the carrageenan content in the system.

Cation effect on thermal transition of iota-carrageenan: a photon transmission study.

Coil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in various cation (CaCl2) solutions upon heating and cooling were studied using the photon transmission technique. Photon transmission intensity, Itr, was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (Tch and Thd) and activation energies (DeltaEch and DeltaEhd). An extra dimer-to-dimer (d-d) transition was observed during cooling at low temperature region. However, upon heating dimers directly decompose into double helices by making dimer-to-double helix (d-h) transition. Further heating results in double helix-to-coil (h-c) transition at high temperature region. Tdh and Thc temperatures and Delta Edh and DeltaEhc activation energies were determined. It was observed that Thc and Tch temperatures and DeltaEch and DeltaEhc activation energies were found to be strongly correlated to the CaCl2 content in the system.