Assessing hydrophobic deep eutectic solvents for intramolecular excimer formation.

Intramolecular excimer formation by a dipyrenyl probe, 6-(1-pyrenyl)hexyl-11(1-pyrenyl)-undecanoate [1-Py(CH2)10COO(CH2)61-Py], is used to assess hydrophobic deep eutectic solvents (HDESs) for the purpose. n-Decanoic acid (DA), L(-)-menthol (Men) and thymol (Thy) have been utilized to form HDESs with different pairs of constituents in different molar ratios, namely Men : DA (2 : 1, 1 : 1, and 1 : 2), Thy : DA (2 : 1, 1 : 1, and 1 : 2), and Thy : Men (5 : 1, 2 : 1, 1 : 1, 1 : 2, and 1 : 5). The maximum of the excimer-to-monomer emission intensity ratio, (IE/IM)max, is observed at 343.15-353.15 K for all DESs irrespective of the constitution, and it varies in a narrow range exhibiting no correlation with the dynamic viscosity (η) of the DES which varies between 2.05 and 3.56 mPa s. Excited-state intensity decay data reveal excimer dissociation back to the excited monomer to be negligible in all DESs at lower temperatures (T ≤ 323.15 K); the simplistic Birks scheme is followed at higher temperatures (T > 323.15 K). The rate constant for excimer formation/association, ka, ranges from (3.00 ± 0.50) × 106 s-1 to (103 ± 10) × 106 s-1, which is similar to that reported in other media. The temperature-dependence of the equilibrium constant for excimer formation follows the van't Hoff equation with recovered standard enthalpy (ΔaH*⊖) and standard entropy (ΔaS*⊖) changes, indicating the reversible intramolecular excimer formation to be exothermic and energetically-favorable but entropically unfavorable. A plot of kavs. T/η for all the DES systems investigated exhibits a fairly good linear correlation, indicating the adherence to the Stokes-Einstein formulation within the HDESs further emphasizing the homogeneous nature of the solubilizing media. The work helps to highlight the potential of HDESs for intramolecular excimer formation involving non-polar reactants.

An Analysis of the VELNEZ Nasal Pack's Acceptability and Safety for Use During Nasal Surgery: A Prospective Study.

The primary function of nasal packs is to modulate the bleeding, prevent adhesions and obstruction, with least discomfort to the subjects without risking secondary infection. However, both packing and removal of the pack is an unpleasant experience, with the latter being extremely painful. Therefore the need of the hour is a dressing which prioritizes subject comfort without compromising other desired nasal pack properties. Twenty subjects were enrolled in this interventional, open label study. The subjects had 10 hospital visits, starting from baseline (Visit 1) to postoperative day 28 (Visit 10), at regular intervals. The proportion of the population with postoperative pain alleviation and bleeding control failure (within 10 min) were the main objectives. Within 10 min of VELNEZ administration, all 20 participants got their bleeding under control. With VELNEZ, the painful nasal pack removal method was totally avoided because it was biodegradable. No moderate/severe pain, infection and adhesions were reported in any of the subjects, but few subjects reported moderate obstruction until Visit 3 (Discharge Day). In the present study, for participants undergoing nasal surgery, VELNEZ proved to be a secure and reliable nasal pack. Trial Registration: CTRI/2021/09/036437, prospectively registered.

Formation of Ethanolamine-Mediated Surfactant-Free Microemulsions Using Hydrophobic Deep Eutectic Solvents.

Hydrophobic deep eutectic solvents (HDESs) are emerging as versatile, relatively benign, and inexpensive alternatives to conventional organic solvents in a diverse set of applications. In this context, the formation of microemulsions with HDES replacing the oil phase has become an area of active exploration. Because of recent reports on the undesirable toxicity of many common surfactants, efforts are under way to investigate the formation of surfactant-free microemulsions (SFMEs) using HDES as an oil phase. We present SFME formation using HDESs constituted of n-decanoic acid and five (5) structurally different terpenoids [thymol, l(-)-menthol, linalool, ß-citronellol, and geraniol] at a 1:1 molar ratio as the oil phase and water as the hydrophilic phase. Ethanolamine (ETA) exhibited the best potential as a hydrotrope among several other similar small molecules. Results showed a drastic increase in water solubility within the HDESs in the presence of ETA. ETA exerted its hydrotropic action at different extent for each DES system via chemical interaction with the H-bond donor (HBD) constituent of the HDES. The optimum hydrotropic concentration (minimum hydrotrope and maximum water retention, XETAOPT) assigned for each DES/ETA/water system and water loading are reported, and the trends are discussed in detail. Ternary phase diagrams are constructed using visual observation and the dye staining method. The area under the single- and multiple-phase regions (assigned in ternary phase diagrams) was estimated. "Pre-Ouzo" enforced by ETA was investigated using dynamic light scattering (DLS) of the DES/ETA/water systems at XETAOPT. A systematic growth in nanoaggregates was observed with the subsequent addition of water in DES/ETA systems while continuously changing the existing microstructure. The presence of a core (oil)-shell (water)-like structure as indicated by the fluorescence response of Nile red in the "pre-Ouzo" region is speculated. We were able to prepare a homogeneous solution of [K3Fe(CN)6] salt in "pre-Ouzo" mixtures with no apparent deviation in the Beer-Lambert law.

Correlation of solute diffusion with dynamic viscosity in lithium salt-added (choline chloride + glycerol) deep eutectic solvents.

Due to their favorable physicochemical properties, deep eutectic solvents (DESs) are finding increased use in chemistry. Metal salt-added DESs are currently being investigated for their potential applications in electrochemistry as a replacement for organic electrolytes. Insights into solute diffusion in salt-added DESs, in this context, are of the utmost importance. Solute diffusion in a LiCl-added DES composed of the H-bond acceptor choline chloride and the H-bond donor glycerol in a 1 : 2 mole ratio, named glyceline, is assessed as a function of temperature and LiCl concentration. For relative translational diffusion, the fluorophore-quencher pair of pyrene-nitromethane is used, whereas for rotational diffusion a fluorescent anisotropic rotor, perylene, is selected. The fluorescence quenching of pyrene by nitromethane was found to be purely dynamic in nature. The estimated bimolecular quenching rate constant (kq) exhibits excellent adherence to the Stokes-Einstein relation, suggesting relative translational diffusion of the solute to be controlled by the dynamic viscosity of the LiCl-added glyceline solution. The rotational reorientation time (θ) of the rotor perylene is also found to scale with dynamic viscosity and obey the Stokes-Einstein relation satisfactorily. Linear correlation between θ and dynamic viscosity (η) improves for glyceline solutions with fixed LiCl concentrations hinting at the possible change in the hydrodynamic volume with LiCl concentration within the DES. Control of rotational diffusion of the solute by the dynamic viscosity is established nonetheless. The effect of earlier reported micro- and/or nano-heterogeneities within salt-added DES systems on solute diffusion dynamics is found to be minimal. The work highlights DESs in offering a solubilizing medium for solutes where the diffusion dynamics are simply controlled by the dynamic viscosity.

Highly Efficient Intramolecular Excimer Formation in a Disulfide-Linked Dipyrenyl Compound: Proton Recognition and Fluidity Assessment.

Intramolecular excimer formation has been utilized extensively in chemical sciences, especially to probe solvation within complex media as well as to assess physicochemical properties of the solubilizing milieu. Pyrene has been employed extensively as a fluorescence probe for this purpose due to its favorable multidimensional fluorescence properties. Termini-capped dipyrenyl scaffolds possessing various functionalities comprise the majority of such compounds. A new both end-tagged dipyrenyl compound DTP is designed and synthesized, which exhibits significantly high intramolecular excimer formation efficiency in polar solvents. The presence of a -NH-(CO)- and/or -S-S- functionality on the chain linking the two pyrenyl groups facilitates intramolecular excimer formation. Excited-state emission intensity decay reveals that the excimer formation exclusively takes place in the excited state with only one excimer conformation. The rate constant of excimer formation is found to be higher for DTP as compared to a similar compound with an alkyl backbone. The dependence of the excimer formation on the solvent (protic versus aprotic) as well as on temperature reveals further insights into the excimer formation process. The excimer formation by DTP is found to be highly sensitive to the presence of H+: the relative excimer formation efficiency decreases drastically in the presence of a small amount of H+ (∼10-5 M). Further, the recognition of protons by DTP via intramolecular excimer formation is also observed to be highly selective in nature. Based on the observation that both the excimer formation efficiency and kinetics depend on the viscosity of the solubilizing milieu, fluidity assessment of the (dimethyl sulfoxide + acetonitrile) mixture was carried out using DTP. Further, DTP is found to be an effective probe for the assessment of the amount of water in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide as well as in a deep eutectic solvent composed of choline chloride and urea in a 1:2 mol ratio. Highly efficient and rapid intramolecular excimer formation not only establishes DTP as a useful and versatile probe but also offers strategic pathways for designing effective excimer-forming compounds.

Intramolecular dimer formation reveals anomalous solvation within fluorous solvent perfluorodecalin.

Due to the unusual properties of fluorine, a fluorous solvent obtained by replacing hydrogen atoms with fluorine atoms in a hydrocarbon solvent may afford unusual solute solvation and aggregation. A fluorescent dipyrenyl probe, 1,3-bis(1-pyrenyl)propane (BPP), was utilized to explore intramolecular aggregation within perfluorodecalin (PFD), a prototypical fluorous solvent. Steady-state fluorescence emission and excitation along with excited-state emission intensity decay of BPP were acquired in the temperature range of 293.15 to 333.15 K in fluorous solvent PFD and n-hexane-added PFD. The probe BPP is known to form an intramolecular excimer in common hydrocarbon solvents, which is characterized by a broad structureless low-energy emission band; the formation of intramolecular excimers exclusively in the excited state was confirmed via excitation scans along with the intensity decay of the monomer and excimer, respectively. While intramolecular dimerization of BPP does occur in PFD, emission wavelength-dependent excitation spectra and fits of the intensity decay data reveal that intramolecular aggregation takes place in the ground state as well. This ground-state heterogeneity is reduced as the temperature is increased. In the presence of as small as 0.1 mole fraction of n-hexane, the ground-state aggregation vanishes, and intramolecular dimerization again takes place exclusively in the excited state. The data hint at the poor solvation of BPP in PFD to be responsible for intramolecular ground-state aggregation. In PFD-rich (PFD + n-hexane) mixtures, probe pyrene (Py) was found to be preferentially solvated by n-hexane, further corroborating the above-mentioned proposition. Clear differences in solute solvation within a fluorous solvent as compared to hydrocarbon solvents leading to unexpected solubilization and aggregation in fluorous media are amply demonstrated.

Fluorescence of pyrene and its derivatives to reveal constituent and composition dependent solvation within hydrophobic deep eutectic solvents.

Depending on their constituents and composition, deep eutectic solvents (DESs) may exhibit widely varying physicochemical properties. Based on the miscibility of water in a DES, it can broadly be classified as 'hydrophobic' or 'hydrophilic'. The polarity offered by hydrophobic DESs as compared to common organic solvents in the context of solute solubilization thus becomes of the utmost importance. A versatile fluorescence probe, pyrene (Py), its aldehyde derivative, pyrene-1-carboxaldehyde (PyCHO), and a termini end-tagged dipyrenyl polydimethylsiloxane polymer (Py-PDMS-Py) are employed to assess the solvation environment afforded by DESs composed of thymol (Thy), (-)-menthol (Men), and n-decanoic acid (DA). To decipher the effect of the constituents and composition on solute solvation, DESs composed of different pairs of constituents in different molar ratios, namely Thy : Men (1 : 1 and 1 : 2), DA : Men (1 : 1 and 1 : 2), and Thy : DA (2 : 1, 1 : 1, and 1 : 2), are investigated. Pyrene, through its band 1-to-band 3 emission intensity ratio (Py I1/I3), displays higher cybotactic region dipolarity in Thy-containing DESs due to the phenyl ring of Thy; the sensitivity of Py I1/I3 towards temperature is also higher in Thy DESs. The fluorescence lifetime of pyrene and its temperature dependence are higher in Men-containing DESs in comparison. Quenching of pyrene fluorescence by nitromethane in these DESs is dynamic in nature and the recovered bimolecular quenching rate constants (kq) reveal efficient diffusion of the fluorophore-quencher pair in these DESs as compared to other iso-viscous media. The kq adheres to the Stokes-Einstein relation, implying inherent homogeneity associated to these DESs. PyCHO emission spectra show a high energy structured band in Thy : Men DESs, whereas the band shifts bathochromically and becomes broad in DA-containing DESs. The PyCHO cybotactic region is relatively nonpolar in Thy : Men DESs as compared to Thy : DA and Men : DA DESs. The extent of intramolecular excimer formation by Py-PDMS-Py reveals these DESs to be "good" solvents for polymer solvation where DES-polymer interactions are maximized. The microviscosity (ηµ) surrounding Py-PDMS-Py correlates with the bulk dynamic viscosity (ηbulk) within the investigated DESs, further corroborating the absence of microheterogeneity. Overall, the observations reveal the similarity of these hydrophobic DESs to common organic solvents in the context of solute solubilization.

Prospective Use of Probiotics to Maintain Astronaut Health during Spaceflight.

Maintaining an astronaut's health during space travel is crucial. Multiple studies have observed various changes in the gut microbiome and physiological health. Astronauts on board the International Space Station (ISS) had changes in the microbial communities in their gut, nose, and skin. Additionally, immune system cell alterations have been observed in astronauts with changes in neutrophils, monocytes, and T-cells. Probiotics help tackle these health issues caused during spaceflight by inhibiting pathogen adherence, enhancing epithelial barrier function by reducing permeability, and producing an anti-inflammatory effect. When exposed to microgravity, probiotics demonstrated a shorter lag phase, faster growth, improved acid tolerance, and bile resistance. A freeze-dried Lactobacillus casei strain Shirota capsule was tested for its stability on ISS for a month and has been shown to enhance innate immunity and balance intestinal microbiota. The usage of freeze-dried spores of B. subtilis proves to be advantageous to long-term spaceflight because it qualifies for all the aspects tested for commercial probiotics under simulated conditions. These results demonstrate a need to further study the effect of probiotics in simulated microgravity and spaceflight conditions and to apply them to overcome the effects caused by gut microbiome dysbiosis and issues that might occur during spaceflight.

Constituent- and Composition-Dependent Surfactant Aggregation in (Lanthanide Salt + Urea) Deep Eutectic Solvents.

Due to the ease of tailoring the physicochemical properties by simply changing a constituent or composition, deep eutectic solvents (DESs) possess widely varying capabilities for surfactant self-assembly that could depend on the surfactant headgroup charge. The self-aggregation process of three surfactants, sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), and Triton X-100 (TX-100), dissolved in DESs composed of a lanthanide salt (Ln) and urea (U) is investigated. The role of the identity of the metal salt is assessed by using [La(NO3)3·6H2O] (La) and [Ce(NO3)3·6H2O] (Ce) and that of the composition is deciphered by systematically changing the mole ratio of the metal salt and urea in (La/U) DESs. The response to a fluorescence probe pyrene-1-carboxaldehyde along with electrical conductance and surface tension measurements is used to obtain the critical aggregation concentration (CAC). While the CACs in 1:3.5 (Ln/U) for SDS are significantly lower than that in water, the values are marginally higher for CTAB and TX-100. The CACs for all three surfactants are similar in 1:3.5 (La/U) and (Ce/U) DESs, implying that the identity of the metal in the salt is not so important. Increasing the urea composition in (La/U) DESs results in increased CAC for SDS and CTAB; however, a minimal decrease in CAC is observed for TX-100. From the temperature dependence of CAC, thermodynamic parameters, ΔGagg0, ΔHagg0, and ΔSagg0, of the surfactant self-aggregation process are estimated. These parameters reveal that while at a lower urea content, the SDS/CTAB self-assembly process is enthalpically driven, it becomes entropically favored at higher urea concentrations. The TX-100 self-aggregation in these DESs is found to be strongly enthalpically favored and entropically un-favored. These parameters are explained as a combination of passage of the solvophobic surfactant chain from the bulk DES to the aggregate pseudo-phase and differential orientation/organization of DES constituents around surfactant monomers and/or aggregates.

Pyrene aggregation at unprecedented low concentrations in (lanthanide metal salt + urea) deep eutectic solvents.

We report intermolecular excimer formation by a common and popular polycyclic aromatic hydrocarbon pyrene at very low concentrations (low µM) when dissolved in deep eutectic solvents constituted of hydrated lanthanide salts and urea. Pyrene is not known to aggregate at such low concentrations in isotropic solvents and common liquids under similar conditions.

Classifying deep eutectic solvents for polymer solvation via intramolecular dimer formation.

Deep eutectic solvents (DESs) have emerged as versatile and inexpensive solubilizing media with widely varying physicochemical properties. Establishing the characteristics of a novel solvent milieu for polymer dissolution is an important exercise. The assessment of two DESs obtained by mixing choline chloride (ChCl) salt with H-bond donors (HBDs) glycerol (Gly) and urea in a 1 : 2 molar ratio (named ChCl:Gly and ChCl:urea, respectively) as solvents for polydimethylsiloxane (PDMS) solvation is carried out via the investigation of intramolecular dimerization by pyrene (Py) end-tagged PDMS of MW 3100 (Py-PDMS-Py) as a fluorescent probe in the temperature range of 293.15-363.15 K. The outcomes are compared with those in liquid PDMS of average MW 2000 (PDMS2000; a similar solvent to that of the polymer) and in glycerol (the HBD constituent of the DES ChCl:Gly). While the intramolecular dimerization by Py-PDMS-Py occurs exclusively in the excited state in liquid PDMS2000, wavelength-dependent fluorescence excitation spectra along with excited-state intensity decay kinetics reveal the presence of ground-state interactions between the pyrenyl moieties in ChCl:Gly, ChCl:urea and glycerol. This leads to the proposition that PDMS prefers to stay in predominantly the coiled form in DESs and glycerol, as opposed to that in PDMS2000 where the PDMS-PDMS contact is maximized leading to the absence of ground-state heterogeneity. Thus, while the liquid PDMS2000 is characterized as a 'good' solvent, the DESs ChCl:Gly and ChCl:urea along with glycerol may be designated as 'bad' solvents for PDMS dissolution.

Ratiometric Recognition of Protons by a Multiple Tagged Designer Fluorescent Chemosensor.

Molecular architecture with different fluorophoric units can offer improved and effective recognition of biologically important analytes. We present here a new strategy for the design of ratiometric chemosensors that operate by photoinduced electron transfer (PET). This ratiometric sensor endowed with tryptophan and anthracene exhibits high sensitivity, excellent selectivity and remarkable reversibility towards recognition of H+ in methanol. This "Turn-On" type behaviour is crafted into the molecule by incorporation of bispidine entity. Effective quenching of the fluorescence of the anthracene by the adjacent amine groups of the bispidine results in negligible fluorescence from the anthracene group leading to highly sensitive recognition of protons by the compound as H+ protonate the amine functionalities giving rise to the emergence of the fluorescence from the anthracene group. This, combined with the reduction in the fluorescence from the Trp group by H+, results in highly sensitive ratiometric nature of the response especially at low [H+].

Contrasting ground- and excited-state intramolecular aggregation in choline chloride-based deep eutectic solvents versus a liquid polymer.

Although the pyrenyl (Py) groups in several dipyrenyl (or bispyrenyl) compounds do not dimerize in the ground-state, they are known to intramolecularly aggregate exclusively in the excited-state to form excimers in common organic solvents. We present contrasting intramolecular aggregation behaviour of such a prototypical compound, 1,3-bis(1-pyrenyl)propane [1Py(3)1Py], dissolved in judiciously selected liquids having relatively high dynamic viscosities (η). Specifically, the intramolecular aggregation of 1Py(3)1Py is investigated in a liquid polymer polydimethylsiloxane with number average MW 2000, PDMS2000 (η293.15K = 21.4 mPa s), and is compared with aggregation of 1Py(3)1Py in deep eutectic solvents (DESs) constituted of the H-bond acceptor (HBA) choline chloride (ChCl) and H-bond donors (HBDs) urea and glycerol in a 1 : 2 mole ratio of ChCl : urea (η293.15K = 1372.0 mPa s) and ChCl : Gly (η293.15K = 473.0 mPa s), respectively, in 293.15 to 363.15 K temperature range. The HBD constituent of ChCl : Gly, glycerol (Gly) (η293.15K = 1412.0 mPa s) is also investigated for comparison purposes. It is found that while in PDMS2000, 1Py(3)1Py intramolecularly aggregates exclusively in the excited-state, thus forming a classical excimer, ground-state heterogeneity is clearly evident in both the DESs and Gly. High viscosity, a consequence of the extensive H-bonding in DESs/Gly, appears to induce the two Py units, both in the ground-state, to exist partly in a configuration where the interaction, albeit a weak one, takes place between the two. This ground-state interaction is not present in relatively low viscosity media PDMS2000 as observed in the common organic solvents. The role of viscosity/H-bonding of the solubilizing milieu on differential intramolecular aggregation in ground- and excited-states is highlighted.

Mesenchymal stem cells are prospective novel off-the-shelf wound management tools.

Chronic/non-healing cutaneous wounds pose a debilitating burden on patients and healthcare system. Presently, treatment modalities are rapidly shifting pace from conventional methods to advanced wound care involving cell-based therapies. Mesenchymal stem cells (MSCs) have come across as a prospective option due to its pleiotropic functions viz. non-immunogenicity, multipotency, multi-lineage plasticity and secretion of growth factors, cytokines, microRNAs (miRNA), exosomes, and microvesicles as part of their secretome for assisting wound healing. We outline the therapeutic role played by MSCs and its secretome in suppressing tissue inflammation, causing immunomodulation, aiding angiogenesis and assisting in scar-free wound healing. We further assess the mechanism of action by which MSCs contribute in manifesting tissue repair. The review flows ahead in exploring factors that influence healing behavior including effect of multiple donor sites, donor age and health status, tissue microenvironment, and in vitro expansion capability. Moving ahead, we overview the advancements achieved in extending the lifespan of cells upon implantation, influence of genetic modifications aimed at altering MSC cargo, and evaluating bioengineered matrix-assisted delivery methods toward faster healing in preclinical and clinical models. We also contribute toward highlighting the challenges faced in commercializing cell-based therapies as standard of care treatment regimens. Finally, we strongly advocate and highlight its application as a futuristic technology for revolutionizing tissue regeneration.

Effect of lithium salt on fluorescence quenching in glycerol: a comparison with ionic liquid/deep eutectic solvent.

It was reported earlier that the addition of LiCl to the deep eutectic solvent (DES) ChCl:Urea (composed of the salt choline chloride and the H-bond donor urea in 1 : 2 molar ratio) and the addition of LiTf2N [Tf2N:(CF3SO2)2N] to the ionic liquid (IL) [C2C1im][Tf2N] ([C2C1im]:1-ethyl-3-methylimidazolium), respectively, results in an increase in the dynamic viscosity of the medium. However, as the concentration of the Li salt is increased, instead of decreasing, the bimolecular quenching rate constant (kq) for the quenching of pyrene fluorescence by nitromethane is observed to first increase and only then decreases within both media. This unusual initial increase in quenching is hypothesized to be due to structural changes in the DES ChCl:Urea and the IL [C2C1im][Tf2N], respectively, as the Li salt is added. We tested this hypothesis by comparing the physical properties and fluorescence quenching behavior between 1 wt% water in glycerol solution which has similar viscosity to that of the DES ChCl:Urea with the aforementioned DES and IL in the presence of lithium salt as media. In complete contrast, irrespective of the temperature, kq is found to decrease monotonically with increasing concentration of LiCl within 1 wt% water in glycerol media. These findings therefore highlight the unusual characteristics of ILs and DESs as solubilizing media. The ionic nature of the IL and the high concentration of ions in the DES are deemed responsible for these outcomes.

Donor-acceptor complex formation in tetra-n-butylammonium chloride: n-decanoic acid deep eutectic solvent.

Complex formation between pyrene (Py) and N,N-dimethylaniline (DMA) is presented in a deep eutectic solvent constituting of tetra-n-butylammonium chloride (TBAC) and n-decanoic acid (DA) in a 1:2 mol ratio, respectively, named TBAC:DA. The addition of DMA to a Py solution of TBAC:DA results in the formation of a fluorescent Py-DMA charge-transfer complex, which is manifested via a broad structureless bathochromically shifted band centered at 550(±2) nm. The solvatochromic nature of the Py-DMA fluorescent complex indicates the solvent polarity of TBAC:DA to be higher than that of methanol. The absence of a negative pre-exponential factor in the intensity decay at 550 nm combined with the excitation scans implies the presence of weak interaction between Py and DMA in the ground-state, leading to the rapid formation of a Py-DMA complex possibly at a sub-nanosecond time scale. The Stern-Volmer quenching constant (KSV) varies from 53(±2) to 96(±1) M-1, and the bimolecular quenching rate constant (kq) varies from 3.0(±0.4) × 108 to 8.8(±1.3) × 108 M-1 s-1 by increasing the temperature (T) from 283.15 to 313.15 K, implying efficient deactivation of electron-acceptor Py in the excited-state induced effectively by the electron-donor DMA within TBAC:DA. ln kq varies linearly with 1/T with an activation energy (Ea) of 26.4(±0.4) kJ mol-1. The linear behavior between kq and 1/η suggests conformity to the Stokes-Einstein relationship within TBAC:DA. The Py-DMA complex formation efficiency increases with an increase in T and reaches maxima at 298.15 K before decreasing with a further increase in T. The initial reduction in η favors Py-DMA complex formation; this effect is overcome by preferential thermal deactivation of the Py-DMA fluorescent complex as compared to that of pyrene.

Ionic Liquid-Controlled Shape Transformation of Spherical to Nonspherical Polymersomes via Hierarchical Self-Assembly of a Diblock Copolymer.

Here, we report the self-assembly of poly(ethylene glycol) methyl ether-block-poly(ε-caprolactone) (PEG-b-PCL) copolymer in three ionic liquids (ILs) possessing different cations with common bis(trifluoromethylsulfonyl)imide anion. The observed polymeric nanostructures in ILs were directly visualized by room temperature conventional transmission and field emission scanning electron microscopy and were further examined for their size and shape by dynamic light scattering technique. The results show that through changes in the concentration of PEG-b-PCL and/or changing the solvent by using a different IL, we can effectively induce shape transformation of self-assembled PEG-b-PCL nanostructures in order to generate nonspherical polymersomes, such as worm-like aggregates, stomatocytes, nanotubes, large hexagonal and tubular-shaped polymersomes. These findings provide a promising platform for the design of biodegradable soft dynamic systems in the micro-/nano-motor field for cancer-targeted delivery, diagnosis and imaging-guided therapy, and controlled release of therapeutic drugs for treatment of many diseases. Non-spherical polymersome-based vaccines may be taken up more efficiently, especially against viruses for pulmonary drug delivery than the spherical polymersomes-based.

Formation of water-in-oil microemulsions within a hydrophobic deep eutectic solvent.

Hydrophobic deep eutectic solvents (DESs) as neoteric, non-toxic, and inexpensive media have the potential to replace organic solvents in various aggregation processes. Conventional water-in-oil microemulsions are formed using mostly environmentally unfavorable toxic organic solvents as the bulk oil phase. Evidence of formation of water-in-DES microemulsions is presented. These novel assemblies are formed using a hydrophobic DES constituted of n-decanoic acid (DA) and tetra-n-butylammonium chloride (TBAC) in 2 : 1 mole ratio, termed TBAC-DA, as the bulk oil phase. It is observed that in the presence of a common and popular non-ionic surfactant Triton X-100 (TX-100), water pools are formed within TBAC-DA under ambient conditions with maximum water loading (w0 = [water]/[TX-100]) of 60 ± 3 for [TX-100] = 300 mM. The formation of the microemulsions is established by using fluorescence probe pyranine, which exhibited the appearance of a band characterizing the un-protonated form of the probe clearly implying onset of water-in-TBAC-DA microemulsion formation. The UV-vis absorbance of CoII further corroborates TX-100-assisted water pool formation within TBAC-DA via the appearance of the band that is assigned to the response of the probe in water. Dynamic light scattering (DLS) measurement suggests average aggregate sizes to be in the range of 72(±4) to 122(±7) nm. These unprecedented water-in-DES microemulsions may have far reaching implications due to their benign nature.

Prototropic forms of hydroxy derivatives of naphthoic acid within deep eutectic solvents.

Deep eutectic solvents (DESs) are not only recognized as benign and inexpensive alternatives to ionic liquids, they offer a unique solvation milieu due to the varying H-bonding capabilities of their constituents. Proton-transfer involving a probe and its prototropic forms strongly depend on the H-bonding nature of the solubilizing media. The presence of prototropic forms of three probes, 1-hydroxy-2-naphthoic acid (1,2-HNA), 3-hydroxy-2-naphthoic acid (3,2-HNA), and 6-hydroxy-2-naphthoic acid (6,2-HNA) is investigated in two DESs, named ChCl:urea and ChCl:glycerol, constituted of H-bond acceptor choline chloride and different H-bond donors, urea and glycerol, respectively, in a 1 : 2 mole ratio under ambient conditions. While 1,2-HNA and 3,2-HNA exhibit an intramolecular H-bonding ability, 6,2-HNA does not. In contrast to common polar solvents, where the monoanionic emitting form of 1,2-HNA is also supported along with the neutral one, in both the DESs only the neutral emitting form exists. Addition of acid to the two DESs, respectively, fail to generate the monocationic form of the probe. Addition of a base to ChCl:urea results in the generation of the monoanionic form; even a very high strength of the base fails to generate the monoanionic emitting form in ChCl:glycerol. Relatively higher H-bond donating acidity of ChCl:glycerol results in added hydroxyl getting involved in H-bonding with alcohol functionalities of ChCl:glycerol leading to the absence of proton extraction to create the monoanionic form of the probe. Only the monoanionic emitting form of 3,2-HNA is present in ChCl:urea; in ChCl:glycerol, due to its higher H-bond donor acidity, the neutral emitting form is also detected. Addition of high strength of acid to ChCl:urea does result in formation of the neutral emitting form. Addition of an aqueous base results in the formation of the dianionic form of 3,2-HNA in ChCl:urea; however, in ChCl:glycerol, the added base fails to convert the neutral form of this probe to the monoanionic form as efficiently as that in ChCl:urea. The monoanionic (carboxylate) form of 6,2-HNA exits in ChCl:urea, whereas the neutral form is present in ChCl:glycerol due to its higher H-bond donating acidity. Addition of an acid can induce a shift in prototropic equilibrium towards the neutral form of 6,2-HNA in ChCl:urea; no change is observed in the behavior of this probe in ChCl:glycerol as the acid is added. Both the DESs support the dianionic form of 6,2-HNA in the presence of the base; the added base helps extract both -OH and -COOH protons of this probe. The H-bond donor component of the DES is clearly established to play a critical role in the prototropic behavior of the probe.

Chitosan and gelatin biopolymer supplemented with mesenchymal stem cells (Velgraft®) enhanced wound healing in goats (Capra hircus): Involvement of VEGF, TGF and CD31.

AIM: Cell-based therapy has emerged as promising strategy for chronic and impaired wounds treatment. Current research is focused on developing biomaterial systems that act as a niche for mesenchymal stem cells (MSCs) to promote wound healing through paracrine molecular cascading. This study was aimed to evaluate the wound healing potential of Velgraft, a ready-to-use biodegradable artificial skin substitute, on excision wound in goats. MATERIALS AND METHODS: Twelve male goats were randomized divided in to three groups of four animals each. After infliction of surgical wound, Velgraft and Soframycin were applied on wounds of the animals of Groups II and III while Group I (sham operated) served as control. Wound diameters were measured at pre-defined time-points for determination of progressive wound healing up to 28 days. Skin sections were stained using Hematoxylin and eosin (H&E) for examining the histoarchitectural changes, Masson trichome staining for ascertaining collagen synthesis and immunohistochemistry for expression of CD31, VEGF and TGF-ß1 proteins to determine post-treatment angiogenesis in the inflicted wounds. RESULTS: Velgraft application appreciably enhanced wound closure by day 21 which was confirmed through restoration of the normal skin architecture as evident based on histopathological examination and characterized by complete regeneration of epidermal layers, collagen fibers, blood capillaries and hair follicular formation. Stimulation of angiogenesis markers was also observed at different time-points post-Velgraft application; which is suggestive of the improved angiogenesis and vasculogenesis. CONCLUSION: Velgraft facilitates wound healing by augmenting early wound closure, enhancing collagen synthesis and deposition, trichosis development and promoting revascularization and epidermal layers restoration.