Co-Solutes Induced Changes in the Properties of Polymeric Solution and Water Dynamics.

In this paper we are addressing the co-solute-induced changes in the properties of an aqueous solution of a block copolymer. Due to the preferential interaction of different co-solute with different regions of the block copolymer, the changes were observed in both the physical properties and water dynamics. The modulation of both the physical properties and water dynamics was monitored using different spectroscopic techniques. Different co-solutes affect micellar properties of copolymer to a different extent signifying their interactions with different regions within the copolymer. The solvent relaxation dynamics were also modulated with the additions of different co-solutes. The change in free-energy (ΔGbf) and rate constant for bound to free water interconversion (kbf) in a copolymeric micelle was calculated which gets affected by the addition of co-solutes. The calculated kbf suggests that betaine, sarcosine, TMAO, and GnHCl favor the ordering of water molecules around the micelle and are excluded from the micellar surface whereas, urea favors the formation of free-water molecules rather than the structurally ordered bound water molecules around the micelle by accumulating at the micellar surface. Among the added methylamines trimethylamine N-oxide affected the water dynamics and its kinetics most profoundly. The protective property of GnHCl was revealed.

Graphene Oxide-Induced Prototropism and Enhancement of Fluorescence Yield of Organic Molecules in Solutions: Recent Advances.

Till date, humankind has mainly acknowledged the quenching phenomenon of graphene oxide (GO). From a fundamental science standpoint, the unique and dynamic prospects of graphene oxide have been showcased in a brief but concise manner. Worldwide research studies have proven that graphene oxide has tremendous potentiality in showcasing breakthroughs in the fields of both basic science and innovative applications. In this Perspective, the fact that, apart from the very common fluorescence quenching phenomenon, graphene oxide can also enhance fluorescence intensity, promote prototropism, demonstrate aggregation-induced emission, and itself exhibit photoluminescence properties in nonaqueous media has been highlighted. It draws attention to the fact regarding unveiling the unknown properties of graphene oxide that might be useful to scientific communities in upcoming years.

How Polyoxometalate Promote the Aggregation of a Cyanine Dye in the Aqueous Solution of Non-Ionic Copolymers of Varying Hydrophilic-Lipophilic Balance?

The nonradiative pathway leading to the photoisomerization of a cyanine dye is well-established information. However, the modulations induced in the photoisomerization pathway by a Keggin-type polyoxometalate in a confined media is new. Our study reveals that, in the presence of pluronic block copolymers F-108 and P-123, phosphomolybdic acid hydrate (PMA) promotes the aggregation of 3,3'-diethylthiadicarbocyanine iodide (DTDCI). The absorption spectra show a clear indication of a red-shifted trimer band in F-108 and P-123, whereas it is absent in F-127 and P-84. Fluorescence emission studies suggest that, in the presence of PMA, the rate of photoisomerization is accelerated in F-108, P-123, and P-84 micelles, whereas it is retarded in F-127 micelles. Time-resolved studies in the presence of PMA indicate the preference of F-108, P-84, and P-123 toward the trapped conformer of DTDCI, whereas F-127 favors the formation of photoisomer of DTDCI. Our findings imply the importance of the interplay between the hydrophobic and electrostatic interactions between the DTDCI cations and the PMA anions in nonionic micelles of varying hydrophilic-lipophilic balance (HLB). Dynamic light scattering (DLS) data suggest a modulation by PMA in the intermicellar electrostatic repulsions of a hydrophilic copolymer micelle, whereas its unaffected in a hydrophobic copolymeric micelle.

Unraveling the Photoluminescence Properties of a Boron Nitride Nanosheet Dispersed in Different Solvents and Its Application to Generate White Light.

Hexagonal boron nitride (h-BN) is an influential 2D nanomaterial; however, its practical optoelectronic applications rely primarily on controlling the structural defects. The photoluminescence depends explicitly on the developed vacancies and substitutional defects. The present work utilizes the concept of facile liquid-phase exfoliation of hexagonal (h) boron nitride (BN) powder in common organic solvents and cosolvent mixtures to obtain a layered boron nitride nanosheet (BNNS). Although the literature concerning the layered structure of BNNS obtained by different methods is substantial, what is lacking is a detailed photoluminescence study of the layered structure obtained by changing the solvent and cosolvent mixtures, and here lies the novelty of our work. The obtained layered structure was subjected to a detailed photoluminescence study by varying the temperature. We tried to correlate how the defects originating upon changing the solvent and cosolvent affected the photoluminescence of the layered BNNS. The obtained layered structure is suitably supported by optical and electron microscopy images. High-resolution transmission electron microscopy confirm the presence of a few layers, and X-ray photoelectron spectroscopy studies give an idea of the atomic composition of the obtained BNNS. The photoluminescence properties of the obtained BNNS in water were modulated by the addition of two different classes of block copolymers, e.g., Pluronic (F-68, P-407, and P-123) and Tetronic (T-904, T-908, and T-90R4) copolymers. As an application, we were successful in constructing a nanocomposite material made up of a BNNS-copolymer-organic fluorophore to check the possibilities of generating white light.

Solute dynamics of a hydrophobic molecule in a menthol-thymol based type-V deep eutectic solvent: effect of composition of the components.

Type-V deep eutectic solvents (DESs) are a newly emerging unique class of solvents obtained by physical mixing and heating of non-ionic components. These solvents show deviation from the thermodynamic ideality. Compared to type-I to IV DESs, type-V DESs are less explored and their physical chemistry is in its nascent stage. In this work, we have chosen a type-V DES based on menthol-thymol (MT) for our working media. Solvent and rotational dynamics were studied with varying temperature using a well-known solvatochromic probe, Coumarin 153 (C153). We prepared the MT-based DES using a reported procedure at three molar ratios: 1 : 1 (M1T1), 1 : 1.5 (M1T1.5), and 2 : 1 (M2T1) of menthol (M) and thymol (T). Time-resolved emission spectra (TRES) were constructed with varying temperature. Utilizing TRES, the decay of the solvent correlation function (C(t)) was plotted. We have correlated the solvent relaxation time in these DESs as a function of viscosity. The time-resolved anisotropy decays were also collected to perceive the rotational relaxation dynamics of C153 as a function of temperature. The decay of solvent relaxation was found to be bi-exponential, and the average solvation time (〈τs〉) in M2T1 was found to be longer than those of M1T1.5 and M1T1. The rotational reorientation times (〈τrot〉) also follow the same trend. We have analysed the rotational dynamics of C153 in type-V DESs employing the Stokes-Einstein-Debye (SED) hydrodynamic model. The rotational dynamics in DESs demonstrate a good correlation with the SED model with a little deviation. In MT-based DESs, the solute's rotational relaxation times approach hydrodynamic stick boundary condition at low viscosity (or at high temperatures) for all molar compositions. Using the Arrhenius-type equations, we have correlated the activation energies for the rotational motion of C153, along with the viscous flow and non-radiative pathways for all the DESs.

Photoluminescence Properties of Graphene Oxide in Non-Aqueous Solvents.

Detailed attention to the interaction between graphene oxide (GO) and various organic fluorophores has been documented in literature as a result of which the impact of GO on the photophysical properties of the fluorophores is well known to the scientific community. However, the photoluminescence (PL) properties of GO in polar aprotic solvents are yet to be established. In this article, the PL properties of GO in polar aprotic solvents using various spectroscopic techniques have been reported. n-π* transition due to the C=O bonds in the sp3 hybrid regions and π-π* transition due to C=C bonds in the sp2 hybrid are prominent in GO. The presence of quasi-molecules within sp2 -sp3 domains acts as PL centers located in the sp3 matrixes of GO are responsible for the PL properties. This study showcases the presence of multiple emissive states of GO in polar aprotic solvents and conveys the fact that the PL properties of GO are very much wavelength-dependent.

How Kosmotropic and Chaotropic Osmolytes Perturb the Properties of an Aqueous Solution of a Pluronic Block Copolymer?

Poloxamer 407 (P-407) composed of a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) unit has two distinct microenvironments: the interior core formed by the PPG unit and the exterior shell formed by the PEG unit. In this work, we have used two fluorescent molecules coumarin-153 and 8-anilino-1-naphthalene sulfonic acid (ANS) of contrasting natures to characterize and probe the water dynamics in the core and corona regions of the copolymer by means of spectroscopic techniques, namely, absorption, fluorescence, and time-resolved fluorescence emission spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Changes in the surface morphologies were characterized by using microscopic techniques. Further, two classes of osmolytes kosmotropic (betaine and sarcosine) and chaotropic (urea) known to perturb the water structure were added to aqueous solutions of P-407. Our studies reveal that the addition of kosmotropes decreases the critical micelle temperature (CMT) of the copolymer, whereas the chaotropic osmolyte increases the CMT. Steady-state studies reveal that the addition of the osmolytes to the copolymer increases the polarity of the micelle formed and hence results in the red shift in the ANS absorbance maximum. FTIR spectroscopy reveals that kosmotropes interact with the PEG moiety of the copolymer, whereas the chaotrope interacts with both the PEG and PPG moieties of the copolymer. Solvent relaxation studies produced less changes upon the addition of the kosmotropes, whereas a greater change in the relaxation time was observed in the presence of the chaotrope.

Glucose-induced self-assembly and phase separation in hydrophilic triblock copolymers and the governing mechanism.

Poly(ethylene oxide, EO)-poly(propylene oxide, PO)-poly(ethylene oxide, EO)-based triblock copolymers (BCPs) with 80% hydrophilicity stay molecularly dissolved as Gaussian chains at ambient temperature, even at fairly high concentrations (>5 %w/v). This study presents the plausible micellization behaviour of such very-hydrophilic Pluronics® - F38, F68, F88, F98, and F108 - incited upon the addition of glucose at low concentrations and temperatures. The outcomes obtained from phase behaviour and scattering studies are described. At temperatures near to ambient temperature, these BCPs form micelles with a central core made of a PO block, surrounded by a corona of highly hydrated EO chains. The phase transitions in these hydrophilic Pluronics® in the presence of glucose are demonstrated via the dehydration of the copolymer coil, leading to a decrease in the I1/I3 ratio, as determined using fluorescence spectroscopy. The temperature-dependent cloud point (CP) showed a marked decrease with an increase in the PO molecular weight and also in the presence of glucose. The change in solution relative viscosity (ηrel) caused by glucose is due to the enhanced dehydration of the EO block of the BCP amphiphile. Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) investigations suggested that the dimensions of the hydrophobic core increase during the dehydration of the EO-PO blocks upon a temperature increase or after adding varying concentrations of glucose, thereby resulting in a micellar shape transition. It has been observed that added glucose influences the phase behaviour of BCPs in an analogous way to the influence of temperature. Also, plausible interactions between the EO-PO blocks and glucose were suggested based on the evaluated optimized descriptors obtained from a computational simulation approach. In addition, the core-shell blended micelles obtained using these BCPs are successfully utilized for drug (curcumin, Cur) solubilization based on the observed peak intensities from UV-visible spectroscopy. The loading of Cur into glucose-containing and glucose-free hydrophilic Pluronic® micelles shows how the radius of the micellar core (Rc) increases in the presence of glucose, thereby indicating Cur solubility enhancement for the Pluronic® micelles. Various kinetics models were employed, demonstrating a drug release profile that enables this approach to be used as an ideal platform for drug delivery.

Modulation of the Protein-Ligand Interaction in the Presence of Graphene Oxide: a Detailed Spectroscopic Study.

Several applications of graphene oxide (GO) have been established over the years, and it has the potential to be used as a biomedical material. Studying the effect of GO on protein-ligand (small molecules/drugs) complex systems are vital as the mechanisms involved are not well understood. The interaction of GO on the protein-ligand binding is also vital for the preparation of an effective drug carrier in the bloodstream. In this work, we have tried to explore in details the effect of GO on the interaction between a hydrophilic molecule, namely, 7-(N,N'-diethylamino) coumarin-3-carboxylic acid (7-DCA) with human serum albumin (HSA) by employing multispectroscopic, microscopic, calorimetric, and molecular docking studies. We find out that protein-ligand complexes were placed on the GO surface, and GO gives stability to the protein-ligand complex via hydrogen bonding, electrostatic interactions, hydrophobic interactions, and so forth. Due to the presence of a large surface area in GO, it offers a hydrophobic environment, and as a result, the emission maxima of 7-DCA in the ternary complex is more blue-shifted, and the average lifetime becomes higher compared to the binary system. Circular dichroism spectral studies give information about the conformational changes of HSA in the absence and presence of GO when it forms complex with 7-DCA. The fluorescence lifetime imaging study shows the presence of the 7-DCA/HSA complex on the GO sheet. Molecular docking simulation shows that the closest distance between 7-DCA and HSA is 11.9 Å, and the protein interacted with the ligand through hydrogen bonding, hydrophobic interaction, and so forth.

Supramolecular interactions of nonsteroidal anti-inflammatory drug in nanochannels of molecular containers: a spectroscopic, thermogravimetric and microscopic investigation.

Supramolecular host-guest complexation between the nonsteroidal anti-inflammatory drug indomethacin (IMC) and molecular containers were investigated. The weakly fluorescent drug molecule becomes highly fluorescent on complexation with different molecular containers, and time-resolved fluorescence emission spectroscopy reveals that the lifetime components of IMC significantly increase in the presence of molecular containers, compared with the lifetimes in neat water. The respective solid host-guest complexes were synthesised and characterised by Fourier transform infrared and (1) H nuclear magnetic resonance spectroscopic analysis. Microscopy techniques were used to analyse modifications of the surface morphology, owing to the formation of supramolecular complexes. The effect of the molecular container on the optical properties of IMC has also been investigated to determine the effect of nanochannels of different size and structure.

Torsional dynamics of thioflavin T in room-temperature ionic liquids: an effect of heterogeneity of the medium.

The ultrafast excited-state dynamics of a fibril binding dye, thioflavin T (ThT), has been studied in two room-temperature ionic liquids (RTILs): 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and methyltrioctylammonium bis(trifluoromethylsulfonyl)imide. Previously, in most studies, it was observed that the excited-state dynamics of the ThT dye were dependent on the viscosity of the medium. In our study, by using RTILs, we have demonstrated that the excited-state dynamics of ThT are not only viscosity dependent, but also dependent on the heterogeneous nature of the medium. The effect of structural heterogeneity present in neat RTILs on the excited-state dynamics of ThT was observed. For both RTILs, excitation wavelength dependency on the emission properties of ThT was observed.

Effect of nanocavities on the torsional dynamics of thioflavin T in various non-aqueous reverse micelles.

The photophysics of thioflavin T (ThT) were observed in different non-aqueous reverse micelles by using steady state absorption and emission spectroscopy and time resolved fluorescence spectroscopy. We have used glycerol, ethylene glycol, dimethyl formamide, methanol and acetonitrile as polar solvents to form reverse micelles. In all reverse micelles with increase in w (w = [polar solvent]/[AOT]) the fluorescence quantum yield decreased in a regular way. The time resolved fluorescence study of ThT in different reverse micelles shows the similar trend as like above. We had plotted a calibration curve using the fluorescence quantum yield of ThT in glycerol-methanol mixtures vs. viscosity and from that curve we found that ThT faced a greater microviscosity in glycerol pool of AOT/isooctane/glycerol reverse micelles than in the pure glycerol, even at the highest w value. In all reverse micelles the emission quantum yield of ThT was retarded several times compared to neat solvents. We have found that the fluorescence quantum yield of ThT decreased with gradual increase in polarity by studying the emission properties of ThT in dioxane-water mixtures of different polarity.

The photophysics of 7-(N,N'-diethylamino)coumarin-3-carboxylic acid in water/AOT/isooctane reverse micelles: an excitation wavelength dependent study.

In this manuscript we have studied the photophysics of 7-(N,N'-diethylamino)coumarin-3-carboxylic acid (7-DCCA) in water/AOT/isooctane reverse micelles. For this purpose we have used steady state absorption and fluorescence emission spectroscopy and time resolved fluorescence spectroscopy. We have studied the spectral behaviour of 7-DCCA inside the water/AOT/isooctane reverse micelles with variation of excitation wavelength. We have studied the dynamics of solvent and rotational relaxation by using two different excitation wavelengths (λ(exi) = 375 nm and λ(exi) = 405 nm). We have observed the excitation wavelength dependent dynamics of 7-DCCA in the reverse micelles. The fluorescence quantum yield, decay time, solvent relaxation time and rotational relaxation time of 7-DCCA in reverse micelles vary with the excitation wavelength. A two step and wobbling-in-cone model was used to interpret the rotational relaxation dynamics of 7-DCCA in reverse micelles.

Photodynamics of biological active flavin in the presence of zwitterionic surfactants.

In the flavin family of photoactive biomolecules, lumichrome (LM) is a very important compound. It contains a tri-cyclic structure with methyl groups at two sides. It formed by the partial decomposition and biodegradation of riboflavin in both acidic as well as in neutral medium. Herein, we have studied the photophysical properties of LM in the presence of two zwitterionic surfactants, namely dodecyldimethyl(3-sulfopropyl) ammonium hydroxide inner salt (DSB), and tetradecyldimethyl(3-sulfopropyl) ammonium hydroxide inner salt (TSB), having the same head group but a different tail part. We have used steady-state absorption, fluorescence emission, and time-resolved fluorescence emission measurements. We observed that in the presence of zwitterionic surfactant aggregates LM shows excitation and emission wavelength dependent emission properties, which demonstrate the structural changes that take place from one form to another prototropic form of LM molecule. The higher rotational relaxation time of LM in the case of DSB compared to TSB demonstrated that LM is facing more rigid environment in DSB micelles compared to TSB micelles.

Photophysics of thiazole orange in deep eutectic solvents.

Photophysics and torsional dynamics of thiazole orange (TO) as a function of temperature have been studied in two deep eutectic solvents (DESs) using spectroscopic techniques. Two DESs are used as a solvent namely DES-I (choline chloride + urea, mole ratio 1: 2) and DES-II (N,N diethyl ethanol ammonium chloride + urea, mole ratio 1: 2). We explore the influence of DESs on the photophysical properties of TO. The fluorescence quantum yield and fluorescence lifetime of TO decreases with increasing temperature due to thermal deactivation. At higher temperature, fluorescence quantum yield of TO decreases in DESs may be due to the molecular rotor nature of TO, with the benzothiazole and quinoline ring of this dye being able to be rotated relative to each other in the excited state. In these solvents, the free volume idea was found to provide a truthful report of the solvent viscosity-temperature behavior, and the probe torsional dynamics. Fluorescence lifetime imaging microscopy (FLIM) was used to insight and observed the distribution of lifetime of TO in the surface of both DESs. The contact angle was determined to show the hygroscopic nature of the DESs.

Graphene oxide-controlled neutral versus cationic form of a red emitting dye: enhancement of fluorescence by graphene oxide.

Fluorescence enhancement of fluorophores in neat solvent media in the presence of graphene oxide (GO) is less known. It is necessary to re-examine the role of GO from the fundamental scientific viewpoint. Herein, we have reported GO controlled conversion from the neutral to cationic form of a red emitting molecule. Besides this, the switching of the role of GO as an enhancer to a quencher of fluorescence depending on the concentration of GO in the presence of proton accepting solvent media was established. Intermolecular proton transfer from the GO surface to fluorophores is responsible for this phenomenon.

Structural transition dynamics of biologically active flavins in alkylglucoside surfactants aggregates.

The photophysics and structural transition dynamics of a bio-active flavin lumichrome (LM) entrapped in two sugars based neutral surfactants were reported. Sugar-based surfactants, which were used for research purpose are potential environmentally friendly, green alternative amphiphilic surface active substance compared to other kinds of common surfactants. Here, two alkyl glucoside surfactants n-octyl-ß-D-glucopyranoside (OBG) and n-octyl-ß-D-thioglucopyranoside (OBTG) were used. This work is carried out by using steady-state absorption and fluorescence emission spectroscopy along with time-resolved fluorescence emission techniques. Photophysics of LM was modulated several folds in these two sugar-based neutral micelles. LM exhibits excitation and emission wavelength dependent fluorescence properties in these two sugars based neutral micelles. LM confined in the micellar environments exhibited structural transition dynamism, i.e. different kinds of conformers are equilibrated. Herein, different conformers of LM are identified and explained with the help of spectroscopic methods. From the fluorescence anisotropy measurement, it was found that the rotational relaxation time of LM in OBG micelle was more compared to that in OBTG micelle, which indicates that the LM molecule faced much more constrained environment in OBG micellar media.

Graphene Oxide as an Enhancer of Fluorescence.

Solvent-dependent switching of graphene oxide (GO) as fluorescence quencher or enhancer was observed. In some solvents, GO increases the fluorescence yield of a hydrophilic molecule 7-(diethylamino)-coumarin-3-carboxylic acid (7-DCA), and in some solvents GO act as a quencher of fluorescence.

Direct observation of solvation dynamics in an aqueous reverse micellar system containing silver nanoparticles in the reverse micellar core.

In this work we have reported the synthesis of silver nanoparticles in aqueous AOT (dioctylsulfosuccinate, sodium salt) n-heptane reverse micelles and then carried out the study of solvation dynamics keeping the system unaltered, i.e., inside the reverse micelles containing silver nanoparticles. Solvation dynamics and anisotropy studies showed that they were highly affected and became slower in reverse micelles containing silver nanoparticle in comparison to the pure reverse micellar system.

Photophysical studies of a hemicyanine dye (LDS-698) in dioxane-water mixture, in different alcohols, and in a room temperature ionic liquid.

In this paper, we have investigated the photophysics of 1-ethyl-2-(4-(p-dimethylaminophenyl)-1,3-butadienyl)pyridinium perchlorate (LDS-698) molecule in dioxane-water mixture and in a room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]). Both photoisomerization and twisted intramolecular charge transfer (TICT) are possible in this molecule. We have shown that TICT is favorable in this molecule in the dioxane-water mixture and in neat [bmim][BF4]. The change in absorption energy of LDS-698 molecule with mole fraction of water is nonlinear in these systems. The Stern-Volmer plot also deviates from linearity in these systems. This nonlinearity is due to the specific solvation of water molecules in the mixture.