Micelles In Aqueous Solution Research Articles

Folic Acid‐Mediated Reduction‐Sensitive Curcumin Prodrug Enhances the Delivery Performance of Curcumin in Liver Cancer Cells

AbstractIn order to improve the delivery performance of curcumin (CUR) in liver cancer cells, we prepared a targeted and reduction‐sensitive prodrug, folic acid‐polyethylene glycol‐disulfide bond‐curcumin (FA‐PEG‐SS‐CUR). The synthesis involved the conjugation of CUR with NH2‐PEG‐NH2 through a disulfide bond, followed by the connection of CUR‐SS‐PEG‐NH2 to FA‐COOH via acylation. The resultant FA‐PEG‐SS‐CUR prodrug self‐assembled into nano micelles in aqueous solutions, displaying excellent dispersibility with an approximate particle size of 119 nm. In vitro drug release studies demonstrated the sensitivity of FA‐PEG‐SS‐CUR to glutathione (GSH), displaying sustained release performance. After 72 h, FA‐PEG‐SS‐CUR exhibited a drug release rate of 38% at low GSH concentration and 59% at high GSH concentration. Notably, FA‐PEG‐SS‐CUR micelles exhibited favorable biocompatibility. The hemolysis rate resulting from co‐incubation with red blood cells remained below 3%. Furthermore, cytotoxicity experiments unveiled the substantial cytotoxicity of FA‐PEG‐SS‐CUR micelles against HepG2 tumor cells. Cellular uptake studies confirmed the greater internalization of FA‐PEG‐SS‐CUR by HepG2 cells compared to the non‐targeted PEG‐SS‐CUR. The findings highlight the potential of FA‐PEG‐SS‐CUR as an ideal drug delivery system for CUR due to its facile synthesis and strong self‐assembly performance.

Pegylated surfactants based on fatty acids: 12-hydroxystearic acid versus stearic acid

We describe the aqueous behavior of short Polyethylene glycol (PEG) chains of Mw 4 kDa that are either mono-functionalized or di-functionalized by 12-hydroxy stearic acid (HSA), and stearic acid (SA), respectively. The end capping of the chains by the fatty acids is achieved by Steglich esterification, after a step of protection of the 12-OH functional group in the case of HSA. Small Angle Neutron Scattering (SANS) shows that mono-functionalized chains with both SA or HSA sticky ends self-assemble in star micelles in aqueous solution, and interact through repulsive steric interactions. The di-functionalized telechelic chains self-assemble in flower micelles that interact through interactions that are attractive on average due to the formation of bridges by chains that share their both ends in two different micelles. Solutions of telechelic chains undergo a phase separation between a dilute solution of micelles and a dense hexagonal crystalline network of flower micelles above a given polymer concentration threshold. This threshold is lower for SA-PEG-SA than for HSA-PEG-HSA. We postulate that this difference of behavior arises from the formation of hydrogen bonds between the OH groups at the C12 of the alkyl chain in case of HSA that increase the stability of the hydrophobic core of the micelles.

Targeted Delivery of Nanoparticle-Conveyed Neutrophils to the Glioblastoma Site for Efficient Therapy.

Glioblastoma is a common brain tumor that poses considerable challenges in drug delivery. In this study, we investigated the potential of cell-based nanoparticles for targeted drug delivery to the glioblastoma sites. The anticancer drug of temozolomide (TMZ)-loaded T7-cholesterol nanoparticle micelles efficiently delivered nanoparticles to neutrophils and, subsequently, to the tumors. T7 is a cell-penetrating peptide that enhances the delivery of T7/TMZ to the target cells. T7 also serves as a transferrin target peptide, enabling targeted delivery to tumors. T7-conjugated cholesterol can self-assemble into micelles in aqueous solution and attach to the membrane of neutrophils. We confirmed that T7/TMZ nanoparticle micelles were efficiently located inside the neutrophils. Thereafter, T7/TMZ-conveyed neutrophils were administered to a glioblastoma mouse model, enabling neutrophils to penetrate the blood-brain barrier and deliver drugs directly to the tumor site. We evaluated the drug delivery efficiency and therapeutic effects of intravenous injection of T7/TMZ-conveyed neutrophils to a glioblastoma mouse model. These results demonstrate the promising role of neutrophil-based nanoparticle delivery systems in the targeted therapy of glioblastoma.

ZIF-8-mediated block copolymer micelles and its application in drug delivery

Block copolymer micelles have been widely used in drug delivery. Great efforts have been made to optimize the function of block copolymer micelles and further enhance their bioavailability. We propose a means of embedding ZIF-8 in block copolymer micelles to regulate its stability for improving the drug release kinetics. The block copolymer poly (2-(diisopropyl amino-ethyl methacrylate)-block-poly (vinylimidazole-co-poly (ethylene glycol) methyl methacrylate) (PDPA18-b-P(Vim18-co-P(EG)5MA21) (PDPV) bearing imidazole moiety was synthesized through reversible addition-cracking chain transfer (RAFT) polymerization. PDPV can self-assemble into micelles in aqueous solution and then be loaded with doxorubicin (DOX) to obtain DOX@PDPV, followed by Zn coordination to anchor ZIF-8 to the PVim moiety in DOX@PDPV to obtain the final drug delivery system DOX@PDPV@ZIF-8 hybrids. The DOX@PDPV@ZIF-8 hybrids can avoid the influence of the critical micelle concentration (CMC) on it, which was further prevent the premature leakage of DOX under physiological conditions. Furthermore, the pH-responsive properties of PDPA and ZIF-8 facilitated enabled the effective release of DOX in weakly acidic tumor environments. In vitro studies also confirmed that DOX@PDPV@ZIF-8 improved DOX accumulation in cells, leading to the inhibition of cancer cell growth. Therefore, the integrated design provided a promising strategy to regulate the stability of block copolymer micelles, improve drug release kinetics, and ultimately inhibit the growth of cancer cell.

Nanostructured gadolinium(III) micelles: Synthesis, characterization, cytotoxic activities, and MRI applications in vivo

Gadolinium-based contrast agents (GBCAs) are used in around 40 % of MRI procedures. Despite initial perceptions of minimal risk, their long-term use has emphasized the need to reduce toxicity and develop more efficient GBCAs with extended blood retention. Advancements in nanomaterials have led to improved GBCAs, enhancing MRI diagnostics. This study synthesizes and characterizes nanostructured gadolinium(III) micelles as superior MRI contrast agents. The complexes, [Gd(L)2], where L is a ligand of the N-alkyl-N-methylglucamine surfactant series (L8, L10 or L12, L10), form nanostructured micelles in aqueous solution. Gd(L8)2 and Gd(L10)2 relaxivities remained stable across concentrations. Compared to Gd-DTPA, Gd(III) micelles showed enhanced T1-weighted MRI contrast. Gd(L12)2 micelles exhibited cytotoxicity against B16F10 melanoma cells (IC50 42.5 ± 2.2 μM) and L292L929 fibroblasts (IC50 52.0 ± 2.5 μM), with a selectivity index of 1.2. In vivo application in mice brain T2-weighted images suggests nanostructured Gd(III) micelles are promising MRI contrast agents for targeting healthy organs or tumors.

Effect of Micellar Morphology on the Temperature-Induced Structural Evolution of ABC Polypeptoid Triblock Terpolymers into Two-Compartment Hydrogel Network.

We investigated the temperature-dependent structural evolution of thermoreversible triblock terpolypeptoid hydrogels, namely poly(N-allyl glycine)-b-poly(N-methyl glycine)-b-poly(N-decyl glycine) (AMD), using small-angle neutron scattering (SANS) with contrast matching in conjunction with X-ray scattering and cryogenic transmission electron microscopy (cryo-TEM) techniques. At room temperature, A100M101D10 triblock terpolypeptoids self-assemble into core-corona-type spherical micelles in aqueous solution. Upon heating above the critical gelation temperature (T gel), SANS analysis revealed the formation of a two-compartment hydrogel network comprising distinct micellar cores composed of dehydrated A blocks and hydrophobic D blocks. At T ≳ T gel, the temperature-dependent dehydration of A block further leads to the gradual rearrangement of both A and D domains, forming well-ordered micellar network at higher temperatures. For AMD polymers with either longer D block or shorter A block, such as A101M111D21 and A43M92D9, elongated nonspherical micelles with a crystalline D core were observed at T < T gel. Although these enlarged crystalline micelles still undergo a sharp sol-to-gel transition upon heating, the higher aggregation number of chains results in the immediate association of the micelles into ordered aggregates at the initial stage, followed by a disruption of the spatial ordering as the temperature further increases. On the other hand, fiber-like structures were also observed for AMD with longer A block, such as A153M127D10, due to the crystallization of A domains. This also influences the assembly pathway of the two-compartment network. Our findings emphasize the critical impact of initial micellar morphology on the structural evolution of AMD hydrogels during the sol-to-gel transition, providing valuable insights for the rational design of thermoresponsive hydrogels with tunable network structures at the nanometer scale.

UV/esterase dual responsive nanosystems based on protoporphyrin IX-polyethylene glycol monomethyl ether for enhanced photodynamic bactericidal and herbicidal effects

Photoactivated pesticides with high activity, environmental friendliness, and no drug resistance represent the direction of pesticide development. However, poor photostability and lack of targeting ability greatly restrict their practical application. Herein, a novel amphiphilic photoactivated polymeric propesticide was synthesized by conjugation of mPEG with the photo/enzyme-labile o-nitrobenzyl ester group followed by grafting protoporphyrin IX (PpIX), which could self-assemble into photo/esterase responsive polymer micelles in aqueous solutions for a controlled release of PpIX. The fluorescence quenching caused by the aggregation of PpIX into hydrophobic core could enhance its photostability. UV/esterase stimulation could trigger the release of PpIX and restore its photodynamic activity. Compared to a single stimulus, dual stimulation could trigger more PpIX release and resulting in higher photodynamic activity and antibacterial effect. In addition, light exposure also showed little influence on the photodynamic activity and antibacterial effect of the system due to enhanced photostability. Compared with PpIX, the nanosystem exhibited higher wettability and retention ability on plant leaves and could resist rainwater washout. Weed control experiment also demonstrated that the system’s control effect on barnyard grass. Therefore, this study provides new ideas for promoting the application of photoactivated pesticides in the field of plant protection.

Impact of Additive Hydrophilicity on Mixed Dye-Nonionic Surfactant Micelles: Micelle Morphology and Dye Localization.

The nonionic surfactant pentaethylene glycol-monododecylether C12E5 forms micelles in aqueous solutions with a lower critical solution temperature. This characteristic solution behavior of C12E5 is independent of the pH. Such micelles are used to solubilize a large variety of active guest molecules like for instance dyestuffs. An example is an acidic azo dye termed Blue used as a hair colorant. Depending on the pH, Blue gradually changes its hydrophilicity from the protonated BlueH at pH = 2 to the bivalent anion Blue2- at pH = 13 while keeping the shape and size of Blue essentially unchanged. These features of C12E5 and Blue offer the unique chance to investigate the sole impact of a tunable hydrophilicity of a guest molecule on the solution behavior of mixed micelles of the guest and C12E5. Accordingly, the present work establishes a phase diagram of Blue-C12E5 micelles and analyzes their morphology including the spatial distribution of Blue in the micelles as a function of the hydrophilicity of Blue. Small angle neutron scattering reveals the size and shape of the micelles, and detailed contrast matching of the C12E5 supported by 1H NMR with NOESY provided insight into the localization of Blue within the micelles as its hydrophilicity changes.

Elucidating the stabilization mechanism of a K+-depleted c-MYC DNA G-quadruplex in hydrophobic imidazolium-based ionic liquids using spectroscopy coupled with molecular dynamics simulations

Stabilizing native nucleic acid structures is critical for developing nucleic acid-based therapeutics, which have enormous potential in biomedicine for disease prevention, disease treatment and diagnostics. Imidazolium chloride ionic liquids (ImCl ILs) can increase the thermal stability of G-Quadruplex DNA structures. Generally, G-Quadruplex DNA requires K+ (or sometimes Na+) to stabilize their structures via coordination of the guanine bases. In this work we investigated the ability of ImCl ILs to stabilize G-Quadruplex DNA without K+ present. Temperature-dependent CD spectroscopy showed that the ImCl ILs that can form micelles in aqueous solution ([OMIM]Cl and [DMIM]Cl) increase the thermal stability of G-Quadruplex DNA without K+, while the ImCl ILs that do not form micelles ([EMIM]Cl, [BMIM]Cl, and [HMIM]Cl) do not stabilize the structure. Notably, [OMIM]Cl and [DMIM]Cl only stabilize G-Quadruplex DNA at concentrations above their CMC values; at concentrations equal to their CMC values these ILs actually destabilize the structure. MD simulations were performed to elucidate the mechanism of thermal stabilization. Simulations are consistent with experimental results as [DMIM]Cl micelles keep the G-Quadruplex structure stable without K+ present. These results show how ILs can encapsulate and stabilize DNA, which can help guide the development of new strategies for stabilizing DNA and RNA structures at room temperature.

Role of isomers and steric hindrance in the micellization of carboxylated carbosilane surfactants

AbstractA series of carboxylated carbosilane surfactants with methyl, ethyl, branching CH3, phenyl, and cyclohexyl (Me‐Si2C‐COONa, Et‐Si2C‐COONa, Si2C‐La‐COONa, Ph‐Si2C‐COONa, and Cy‐Si2C‐COONa) were prepared. The effect of isomer and steric hindrance on their micellization in aqueous solution was investigated by surface tension, conductivity, transmission electron microscopy (TEM) and dynamic light scattering (DLS). Si2C‐La‐COONa with branching CH3 shows a lower γCMC value and higher the CMC value compared with Et‐Si2C‐COONa. Cy‐Si2C‐COONa with cyclohexyl (41.6 mN m−1) and Ph‐Si2C‐COONa with phenyl (43.9 mN m−1) have larger γCMC values due to the distinct steric hindrance and hydrophobicity. In aqueous solution, the aggregation behavior of Si2C‐La‐COONa, Cy‐Si2C‐COONa, and Ph‐Si2C‐COONa is enthalpy‐driven. However, the micellization process of Me‐Si2C‐COONa and Et‐Si2C‐COONa is governed by the enthalpy‐driven at high temperature and entropy‐driven at low temperature. DLS and TEM results indicate that the carboxylated carbosilane surfactants can self‐assemble into aggregate with hydrodynamic diameters of 50–400 nm.

Development and performance evaluation of self-assembled pH-responsive curcumin-bacterial exopolysaccharide micellar conjugates as bioactive delivery system

The present study reports the synthesis of micellar conjugates, wherein curcumin (Cur), a bioactive compound with poor bioavailability, was covalently bonded to a bacterial exopolysaccharide (EPS). These conjugates were synthesized by utilizing succinic acid that linked Cur to the pyranosyl moiety of the EPS. The Cur-EPS conjugates appeared as spherical micelles in aqueous solution and were found to have an average hydrodynamic diameter of 254 ± 2.7 nm. The micellar conjugates showed superior stability than Cur as evident from their negative surface charge (−27 ± 1.8 mV) and low polydispersity index (PDI) (0.33 ± 0.04). The in vitro studies on release kinetics helped elucidate the pH-responsive characteristics of the Cur-EPS conjugate, as 87.50 ± 1.45 % of Cur was released at an acidic pH of 5.6, in contrast to 30.15 ± 2.61 % at systemic pH of 7.4 at 150 h. The conjugates were hemocompatible and exhibited cytotoxic effect against the osteosarcoma cell line (MG-63) after 48 h treatment. They also demonstrated superior antibacterial, antibiofilm, and antioxidant activities in comparison to free Cur. Therefore, the Cur-EPS conjugates have potential pharmaceutical applications as therapeutic biomaterial that can be applied as a drug delivery system.

Interaction of sodium dodecyl sulfate and cetyl trimethyl ammonium bromide surfactants with amantadine drug in aqueous solution: Conductometric and molecular dynamics studies

In the present work, the interaction of sodium dodecyl sulfate and cetyl trimethyl ammonium bromide surfactants with amantadine drug in aqueous solutions was studied using conductometric measurements and molecular dynamic simulation. Conductometric data were used to determine the critical micelle concentration (CMC) values of surfactants on various amantadine aqueous solutions at T= (300.2, 310.2 and 320.2) K and 0.1 MPa. The effect of amantadine concentration (m = 0.0005, 0.0010, 0.0015 and 0.002 mol.kg−1) on CMC of sodium dodecyl sulfate and cetyl trimethyl ammonium bromide surfactants was investigated. It was observed the CMC value of sodium dodecyl sulfate surfactant increases with increasing of amantadine concentration whereas the CMC values of cetyl trimethyl ammonium bromide surfactant decrease with increasing of amantadine concentration at the same temperature. Then, the thermodynamic properties such as standard Gibbs free energy, enthalpy, and entropy for micellization in aqueous solutions were determined. In addition, molecular dynamic simulation was carried out to understand the interaction sodium dodecyl sulfate and cetyl trimethyl ammonium bromide surfactants with amantadine at the molecular level and microscopic interactions. The root-mean-square deviations and electrostatic, hydrogen binding and hydrophobic interactions were determined by MD simulations. It was seen, the electrostatic and hydrogen bonding interactions play a crucial role in sodium dodecyl sulfate and amantadine aqueous system. The obtained results showed the simulation and experimental data are in agreement with each other.

Synthesis, characterization, antibacterial and antifungal activities of 1-O-alkylglycerols

1-O-alkylglycerols are a class of natural existing lipids with broad biological activities. However, their use in food or agricultural fields remains to be investigated, especially for their antimicrobial activity. In this work, three 1-O-alkylglycerols, 1-O-octanylglycerol (C8Gly1), 1-O-dodecylglycerol (C12Gly1), and 1-O-hexadecylglycerol (C16Gly1), were synthesized in the isolated yields of 71.3–89.8 % and characterized by 1H NMR, 13C NMR, FITR, mass spectra, and HPLC-ESLD. The critical micelle concentration (CMC) of 1-O-alkylglycerols was determined to be 1.65 mmol/L (C8Gly1), 0.33 mmol/L (C12Gly1), and 0.23 mmol/L (C16Gly1) using the pyrene method. C12Gly1 and C16Gly1 had similar surface tensions that are lower than C8Gly1. C8Gly1 can form micelles in aqueous solution with excellent nano-dispersed uniformity and stability. Furthermore, C8Gly1 and C12Gly1 not only displayed good antibacterial activity against Staphylococcus aureus, but they also inhibited the growth of Botryosphaeria dothidea, Monilia fructigena, and Phytophthora capsicum at 400 μg/mL. Thus, the C8Gly1 and C12Gly1 can serve as novel antimicrobial agents in food preservation.

The effect of instrument inertia on the initiation of oscillatory flow in stress controlled rheometry

In a recent paper [Hassager, J. Rheol. 64, 545–550 (2020)], Hassager performed an analysis of the start up of stress-controlled oscillatory flow based on the general theory of linear viscoelasticity. The analysis provided a theoretical basis for exploring the establishment of a steady strain offset that is inherent to stress controlled oscillatory rheometric protocols. However, the analysis neglected the impact of instrument inertia on the establishment of the steady periodic response. The inclusion of the inertia term in the framework is important since it (i) gives rise to inertio-elastic ringing and (ii) introduces an additional phase shift in the periodic part of the response. Herein, we modify the expressions to include an appropriate inertial contribution and demonstrate that the presence of the additional terms can have a substantial impact on the time scale required to attain the steady state periodic response. The analysis is then applied to an aqueous solution of wormlike micelles.

Synthesis and Self-assembly of a Novel Amphiphilic Tri-arm Star-shaped Copolymer Poly(ethylene oxide)-b-Poly(ε-caprolactone)

Abstract:Amphiphilic tri-arm star-shaped copolymers, poly(ethylene oxide)-b-poly(ε-caprolactone) PEO3-b-PCL3, with different poly (ε-caprolactone) (PCL) molecular weights were successfully synthesized by ring-opening polymerization (ROP). Firstly, the tri-arm star-shaped PEO3 was prepared by ROP of trimethylolpropane and ethylene oxide (EO). The ring-opening polymerization (ROP) of ε- caprolactone (CL) was initiated using the tri-arm star-shaped PEO3 with the hydroxyl group as macroinitiator and Sn(Oct)2 as a catalyst. Amphiphilic tri-arm star-shaped copolymers PEO3-b-PCL3 were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO3-b-PCL3 were prepared with a well-defined structure, molecular weight control, and narrow molecular weight distribution. The expected intermediates and final products were confirmed by 1H NMR and Gel Permeation Chromatography (GPC) analyses. In addition, the sizes and morphologies of the obtained micelles with different PCL segment lengths were investigated with dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. It was found that the self-assembly morphologies were spherical micelle in aqueous solution.

New anionic Gemini surfactant viscoelastic fluid for clean fracturing of natural gas hydrate

In this work, the properties of a new anionic Gemini surfactant (AGn) and its application in natural gas hydrate fracturing fluid are studied. The surface properties of AGn were investigated and the formulations of AGn / NH4Cl and AGn / TMBAC (Benzyltrimethylammonium chloride) systems were optimized. The temperature and shear resistance, shear recovery, viscoelasticity, and fracturing performance of the optimized system were evaluated. The results showed that AGn exhibits excellent surface activity and can spontaneously form worm-like micelles in aqueous solution. The optimized fracturing fluid system formulations were 1.5% AG16 + 0.4% NH4Cl and 1.5% AG16 + 0.4% TMBAC. The system had good rheological properties, outstanding filtration, and excellent sand suspension performance, and could complete gel breaking in a 4% NaCl environment. It was suggested that the AGn-based fracturing fluid system has the potential to meet the fracturing requirements of natural gas hydrate fracturing operations and has potential application prospects.

Incorporating Catalytic Units into Nanomaterials: Rational Design of Multipurpose Catalysts for CO2 Valorization.

ConspectusCO2 conversion to valuable chemicals is effective at reducing CO2 emissions. We previously proposed valorization strategies and developed efficient catalysts to address thermodynamic stability and kinetic inertness issues related to CO2 conversion. Earlier, we developed molecular capture reagents and catalysts to integrate CO2 capture and conversion, i.e., in situ transformation. Based on the mechanistic understanding of CO2 capture, activation, and transformation at a molecular level, we set out to develop heterogeneous catalysts by incorporating catalytic units into nanomaterials via the immobilization of active molecular catalysts onto nanomaterials and designing nanomaterials with intrinsic catalytic sites.In thermocatalytic CO2 conversion, carbonaceous and metal-organic framework (MOF)-based catalysts were developed for nonreductive and reductive CO2 conversion. Novel Cu- and Zn-based MOFs and carbon-supported Cu catalysts were prepared and successfully applied to the cycloaddition, carboxylation, and carboxylative cyclization reactions with CO2, generating cyclic carbonates, carboxyl acids, and oxazolidinones as respective target products. Reductive conversion of CO2, especially reductive functionalization with CO2, is a promising transformation strategy to produce valuable chemicals, alleviating chemical production that relies on petrochemistry. We explored the hierarchical reductive functionalization of CO2 using organocatalysts and proposed strategies to regulate the CO2 reduction level, triggering heterogeneous catalyst investigation. Introducing multiple active sites into nanomaterials opens possibilities to develop novel CO2 transformation strategies. CO2 capture and in situ conversion were realized with an N-doped carbon-supported Zn complex and MOF materials as CO2 adsorbents and catalysts. These nanomaterial-based catalysts feature high stability and excellent efficiency and act as shape-selective catalysts in some cases due to their unique pore structure.Nanomaterial-based catalysts are also appealing candidates for photocatalytic CO2 reduction (PCO2RR) and electrocatalytic CO2 reduction (ECO2RR), so we developed a series of hybrid photo-/electrocatalysts by incorporating active metal complexes into different matrixes such as porous organic polymers (POPs), metal-organic layers (MOLs), micelles, and conducting polymers. By introducing Re-bipyridine and Fe-porphyrin complexes into POPs and regulating the structure of the polymer chain, catalyst stability and efficiency increased in PCO2RR. PCO2RR in aqueous solution was realized by designing the Re-bipyridine-containing amphiphilic polymer to form micelles in aqueous solution and act as nanoreactors. We prepared MOLs with two different metallic centers, i.e., the Ni-bipyridine site and Ni-O node, to improve the efficiency for PCO2RR due to the synergistic effect of these metal centers. Sulfylphenoxy-decorated cobalt phthalocyanine (CoPc) cross-linked polypyrrole was prepared and used as a cathode, achieving the electrocatalytic transformation of diluted CO2 benefiting from the CO2 adsorption capability of polypyrrole. We fabricated immobilized 4-(t-butyl)-phenoxy cobalt phthalocyanine and Bi-MOF as cathodes to promote the paired electrolysis of CO2 and 5-hydroxymethylfurfural (HMF) and obtained CO2 reductive products and 2,5-furandicarboxylic acid (FDCA) efficiently.

New Lyotropic Complex Fluid Structured in Sheets of Ellipsoidal Micelles Solubilizing Fragrance Oils.

New lyotropic, fragranced, viscoelastic fluid with a complex structure is obtained from fragranced microemulsions by the addition of a fatty acid. Nonhomogeneous mixing of an appropriate nonionic surfactant, a fatty acid, and a fragrance oil led to the formation of anisotropically shaped and highly oriented micelles in aqueous solution. The nano- and microstructures, and consequently the viscosity, are controlled by the balance of fatty acids used as a cosurfactant and fragrance molecules, which partly behave as a cosurfactant and partly segregate in the micelles of the hydrophilic nonionic surfactant. The transition from isotropic microemulsion to a more structured viscoelastic solution is characterized by X-ray scattering and rheological methods. Considering our X-ray scattering results, we propose a structure composed of planar sheets of ellipsoidal micelles arranged in a lamellar type of stacking. The complex structured, low viscous, transparent fluid is capable of solubilizing a fragrance inside the ellipsoidal micelles, as well as retaining microparticles containing fragrance, without the addition of a polymeric thickener or another gelator. These features allow the creation of a 2-in-1 fragrance-solubilizing liquid product compatible with all types of home and body care consumer products.

Association of bovine serum albumin and cetyltrimethylammonium chloride: An investigation of the effects of temperature and hydrotropes

Interactions between bovine serum albumin (BSA) and cetyltrimethylammonium chloride (CTAC) were studied utilizing conductivity approach. The critical micelle concentration (CMC), micelle ionization (α) along with counter ion binding (β) of CTAC micellization in aqueous solutions of BSA/BSA + hydrotropes (HYTs) have been computed at 298.15−323.15 K. Increase in temperatures of CTAC + BSA/BSA mixtures in HYTs resulted in elevation of CMC due to the association of chemical species in the respective systems which reduced the degree of micelle formation. CTAC + BSA consumed greater extents of surfactant species to generate micelle formation in the corresponding systems at higher temperatures. Standard free energy change ∆Gm0 associated with the assembling processes of CTAC in BSA was found negative suggesting the spontaneous nature of micellization processes. Magnitudes of ∆Hm0 and ∆Sm0 obtained from CTAC + BSA aggregation revealed the existence of H-bonding, electrostatic interactions along with hydrophobic forces among the constituents employed in the respective systems. ∆Gm0 The estimated thermodynamic parameters of transfer (free energy (∆Gm,tr0), enthalpy (∆Hm,tr0) and entropy (∆Sm,tr0)) and compensation variables (∆Hm0,∗ and Tc) provided significant insights on the association behaviors of the CTAC + BSA system in the selected HYTs solutions.

Unraveling the in vivo biological fate of mPEG2000-PDLLA2500-COOH diblock copolymers by LC-MS/MS based on CID in source technique

Methoxy poly (ethylene glycol)-poly(D, L-lactic acid) (mPEG-PDLLA) is a biocompatible and amphiphilic diblock copolymer composed of a hydrophilic poly(ethylene glycol) block and a hydrophobic poly(D, L-lactic acid) block, which can self-assemble into micelles in aqueous solution. It is one of the most widely used diblock copolymers for drug delivery, drug solubilization and drug encapsulation. Fully characterizing the in vivo fate of mPEG-PDLLA diblock copolymers is important to promote the further development of polymer-based nanocarrier drug delivery systems. However, to date, a bioanalysis assay for simultaneous quantification of mPEG-PDLLA and mPEG has not been reported. In this study, we developed such a novel LC-MS/MS assay based on CID in source technique and used it to study the multiple-dose pharmacokinetic, tissue distribution and excretion of mPEG2000-PDLLA2500-COOH and mPEG2000 in rat after intravenous administration. The results indicate that mPEG2000-PDLLA2500-COOH and mPEG2000 are mainly distributed to the liver, lung, spleen and kidney after intravenous administration. mPEG2000-PDLLA2500-COOH is mostly excreted via the renal route in the form of mPEG2000. Overall, the results of this study provide a comprehensive and clear picture of the in vivo fate of mPEG2000-PDLLA2500-COOH which will be useful in evaluating the efficiency and safety of polymer-based nanocarrier drug delivery systems.