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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Investigation of Different Prototropic Forms of Biologically Active Flavin Lumichrome in the Presence of Liposome.

Herein, we reported the photophysical behavior of lumichrome (LC), one of the biologically active flavin molecules, in the presence of small unilamellar vesicle of anionic lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). With the help of different spectroscopic techniques, we have proposed that anionic DMPC liposome interacts with the cationic form LC in ground state and in excited state and modulate the spectral properties of LC. Photophysical study reveals that different prototropic forms of LC are present in DMPC liposome medium. In the presence of DMPC liposome, fluorescence emission properties of LC vary with change in excitation and emission wavelengths. This indicates switch over between different structural forms of LC. From fluorescence lifetime measurements and fluorescence lifetime imaging (FLIM) study, it was revealed that emission decay profile of LC was fitted biexponentially in the presence of liposome. It suggests that in the presence of liposome, more than one form of LC is present. We have constructed the time-resolved area-normalized emission spectra (TRANES) of LC in the liposome and found one isoemissive point. This confirmed that two emissive species of LC are present in liposome. FLIM study and FE-SEM study give an idea about the structural feature of the complex between LC and liposome.

Host-guest interaction of 3-hydroxyflavone and 7-hydroxyflavone with cucurbit [7]uril: A spectroscopic and calorimetric approach.

The modulation of photophysical behaviour of small organic molecules in the presence of macrocycles is one of the most interesting areas of research. In this work we reported the interaction of two biologically active molecules 3-hydroxyflavone and 7-hydroxyflavone with macrocyclic host cucurbit [7]uril in aqueous medium. To investigate the change of photophysical properties of these two flavones, we have used steady state absorption, fluorescence, time resolved fluorescence emission spectroscopy and isothermal titration calorimetric technique. It is observed that on complexation with cucurbit [7]uril, the excited state proton transfer processes in both flavones have been facilitated. Isothermal titration calorimetric method was used in order to investigate the involvement of thermodynamic parameters in complexation between flavone with cucurbit [7]uril. The changes in thermodynamic properties due to the complexation of the flavones molecules with cucurbit [7]urils help to understand about the governing parameters involved in this complexation. The inclusion of flavone molecules inside the cavity of cucurbit [7]uril molecules was studied theoretically to decipher the molecular orientation of flavones in the presence of cucurbit [7]uril. The structure of HOMO and LUMO of the complexes between cucurbit [7]uril with flavones was reported. This study will be helpful to get the knowledge about the modulation of photophysical properties of the flavones molecules on addition of macrocyclic host cucurbit [7]uril. This study will be helpful for the use of cucurbit [7]uril as a potential drug delivery system.

Interaction of Biologically Active Flavins inside Bile Salt Aggregates: Molecular Level Investigation.

In this work we have studied the photophysics of biologically active flavin molecule lumichrome (LCM) in different bile-salt aggregates. With alteration of the functional groups of the bile salts, the photophysics of confined fluorophore is largely affected and shows difference in their spectral behavior. This study also reveals the selective prototropic species of LCM present in bile salt aggregates. In the presence of the bile salt aggregates, LCM molecule shows excitation and emission wavelength-dependent emission properties, indicating switch over of the structural change of different prototropic form of the LCM molecule. The observation of higher rotational relaxation time in NaDC aggregates compared to NaTC aggregates clearly reflects that NaDC aggregates are more rigid due to its greater hydrophobicity and large in size, which is capable to bind the guest molecule more into their nanoconfined medium. Moreover, due to less acidic nature, NaDC aggregates have more ability to accept hydrogen bond from the LCM molecule and show the selective formation of isoalloxazine N10 anion (A1 monoanionic form) of LCM.

Surfactants induced release of a red emitting dye from the nanocavity of a molecular container: A spectroscopic and calorimetric study.

Supramolecular interaction of a red emitting dye Nile blue A (NBA) with Cucurbit[7]uril (CB7) in aqueous solution was studied and the release of the dye from the hydrophobic cavity of CB7 was reported. To investigate the supramolecular host-guest complex formation and release of dye, we have used the steady state absorption, fluorescence and time resolved fluorescence emission spectroscopy, (1)H NMR spectroscopy and isothermal titration calorimetry (ITC). The spectral properties of NBA were changed in the presence of CB7. The change in spectral features of NBA in presence of CB7 indicates the formation of supramolecular host-guest complexes. By using the SED equation the diameter of the complex was estimated. The complex formation further affirmed by the (1)H NMR study. Upfield and downfield shifts of the protons of NBA was observed in both the aliphatic and aromatic region. From the ITC measurement, we have drawn up the forces involved for the complexation of NBA with CB7. We have studied the release of NBA from the hydrophobic cavity of CB7 by using ionic, neutral surfactants and ionic liquid with the help of spectroscopic and calorimetric techniques. It is observed that on addition of SDS and ionic liquid (

Alteration in DNA binding pattern of conformationally locked NC(O)N system: A spectroscopic investigation.

The binding mode of a conformationally locked NC(O)N planar system with deoxyribonucleic acid (DNA) is investigated using various spectroscopic and enzymatic assays. Compound 1 and its four different salts (comp. 2-5) were prepared for this purpose. They showed certain changes in their respective DNA-compound complex at ground state and excited state as measured by UV-vis and fluorescence emission spectra. The Stern-Volmer quenching constant (KSV) for the neutral species (1) is found 8545 M(-1), whereas, for its salts 2, 3, 4 and 5 the quenching constants were 33510 M(-1), 11352 M(-1), 19693 M(-1) and 27270 M(-1) respectively. Nevertheless, the binding constant values remain comparable in neutral and salt forms except for 5. To elucidate the reason we took their CD spectra and ran a topoisomerase I (Topo I) assay. These experimental data revel the fact that compound 1 (neutral form) binds at the minor groove of DNA, whereas, its salt (2) has an extended intercalating property.

Supramolecular interaction of a cancer cell photosensitizer in the nanocavity of cucurbit[7]uril: A spectroscopic and calorimetric study.

The interaction of small biologically active molecules in the nanocavity of supramolecular host is very interesting and thriving research area. In the presence of supramolecular host the absorption and emission properties of small biologically active molecules were modulated several folds compared to bulk solution. In this study we have investigated the supramolecular interaction of a cancer cell photosensitizer molecule harmane in the presence of cucurbit[7]uril (CB7) as host in aqueous buffer solution (pH∼7.2). We have used steady state absorption, emission and time resolved fluorescence spectroscopy techniques. The thermodynamics of the binding between harmane in the nanochannel of CB7 were studied by using isothermal titration calorimetry (ITC) method. The emission properties of harmane are modulated several fold in the presence of CB7. ITC study indicates that the complexation between harmane and CB7 are enthalpically favourable.

Photophysics and Rotational Dynamics of a Hydrophilic Molecule in a Room Temperature Ionic Liquid.

We have studied the photophysics and rotational diffusion of hydrophilic solute 7-(N, N'-diethylamino)coumarin-3-carboxylic acid (7-DCCA) in a room temperature ionic liquid methyltrioctylammonium bis(trifluoromethylsulfonyl) imide ([N1888 ][NTf2 ]). Comparison of activation energies of viscous flow and nonradiative decay shows that the photophysical properties of 7-DCCA are not guided by the bulk viscosity of the medium but are dependent on the specific solute solvent interaction and structural heterogeneity of the medium. The rotational relaxation behaviour of 7-DCCA in [N1888 ][NTf2] shows significant deviation from the Stokes Einstein Debye hydrodynamic model of rotational diffusion. This is indicative of the influence of specific solute solvent interaction on the rotational relaxation behaviour of 7-DCCA. Comparison of activation energy of rotational relaxation with activation energy of viscous flow clearly reinforces our assumption that the structural heterogeneity of the medium and specific solute solvent interaction plays a dominant role on the rotational diffusion instead of bulk viscosity.