Synthesis and Kinetics of CO2-Responsive Gemini Surfactants.

Surfactants are hailed as "industrial monosodium glutamate", and are widely used as emulsifiers, demulsifiers, water treatment agents, etc., in the petroleum industry. However, due to the unidirectivity of conventional surfactants, the difficulty in demulsifying petroleum emulsions generated after emulsification with such surfactants increases sharply. Therefore, it is of great significance and application value to design and develop a novel switchable surfactant for oil exploitation. In this study, a CO2-switchable Gemini surfactant of N,N'-dimethyl-N,N'-didodecyl butylene diamine (DMDBA) was synthesized from 1, 4-dibromobutane, dodecylamine, formic acid, and formaldehyde. Then, the synthesized surfactant was structurally characterized by infrared (IR) spectroscopy, hydrogen nuclear magnetic resonance (1H NMR) spectroscopy, and electrospray ionization mass spectrometry (ESI-MS); the changes in conductivity and Zeta potential of DMDBA before and after CO2/N2 injection were also studied. The results show that DMDBA had a good CO2 response and cycle reversibility. The critical micelle concentration (CMC) of cationic surfactant obtained from DMDBA by injecting CO2 was 1.45 × 10-4 mol/L, the surface tension at CMC was 33.4 mN·m-1, and the contact angle with paraffin was less than 90°, indicating that it had a good surface activity and wettability. In addition, the kinetic law of the process of producing surfactant by injecting CO2 was studied, and it was found that the process was a second-order reaction. The influence of temperature and gas velocity on the reaction dynamics was explored. The calculated values from the equation were in good agreement with the measured values, with a correlation coefficient greater than 0.9950. The activation energy measured during the formation of surfactant was Ea = 91.16 kJ/mol.

Distinct Solubilization Mechanisms of Medroxyprogesterone in Gemini Surfactant Micelles: A Comparative Study with Progesterone.

The solubilization behavior of medroxyprogesterone (MP) within gemini surfactant micelles (14-6-14,2Br-) was investigated and compared with that of progesterone to uncover distinct solubilization mechanisms. We employed 1H-NMR and 2D ROESY spectroscopy to elucidate the spatial positioning of MP within the micelle, revealing that MP integrates more deeply into the micellar core. This behavior is linked to the unique structural features of MP, particularly its 17ß-acetyl group, which promotes enhanced interactions with the hydrophobic regions of the micelle, while the 6α-methyl group interacts with the hydrophilic regions of the micelle. The 2D ROESY correlations specifically highlighted interactions between the hydrophobic chains of the surfactant and two protons of MP, H22 and H19. Complementary machine learning and electron density analyses supported these spectroscopic findings, underscoring the pivotal role of the molecular characteristics of MP in its solubilization behavior. These insights into the solubilization dynamics of MP not only advance our understanding of hydrophobic compound incorporation in gemini surfactant micelles but also indicate the potential of 14-6-14,2Br- micelles for diverse drug delivery applications.

Study on the Synthesis, Surface Activity, and Self-Assembly Behavior of Anionic Non-Ionic Gemini Surfactants.

The use of surfactants in oil recovery can effectively improve crude oil recovery rate. Due to the enhanced salt and temperature resistance of surfactant molecules by non-ionic chain segments, anionic groups have good emulsifying stability. Currently, there are many studies on anionic non-ionic surfactants for oil recovery in China, but there is relatively little systematic research on introducing EOs into hydrophobic alkyl chains, especially on their self-assembly behavior. This article proposes a simple and effective synthesis method, using 3-aminopropane sulfonic acid, fatty alcohol polyoxyethylene ether, and epichlorohydrin as raw materials, to insert EO into hydrophobic alkyl chains and synthesize a series of new anionic non-ionic Gemini surfactants (CnEO-5, n = 8, 12, 16). The surface activity, thermodynamic properties, and self-assembly behavior of these surfactants were systematically studied through surface tension, conductivity, steady-state fluorescence probes, transmission electron microscopy, and molecular dynamics simulations. The surface tension test results show that CnEO-5 has high surface activity and is higher than traditional single chain surfactants and structurally similar anionic non-ionic Gemini surfactants. Additionally, thermodynamic parameters (e.g., ΔG°mic ΔH°mic ΔS°mic et al. indicate that CnEO-5 molecules are exothermic and spontaneous during the micellization process. DLS, p-values, and TEM results indicate that anionic non-ionic Gemini surfactants with shorter hydrophobic chains (such as C8EO-5) tend to form larger vesicles in aqueous solutions, which are formed in a tail to tail and staggered manner; Negative non-ionic Gemini surfactants with longer hydrophobic chains (such as C12EO-5, C16EO-5) tend to form small micelles. The test results indicate that CnEO-5 anionic non-ionic Gemini surfactants have certain application prospects in improving crude oil recovery.

Selective and Efficient CO2 Electroreduction to Formate on Copper Electrodes Modified by Cationic Gemini Surfactants.

Electroreduction of CO2 into valuable chemicals and fuels is a promising strategy to mitigate energy and environmental problems. However, it usually suffers from unsatisfactory selectivity for a single product and inadequate electrochemical stability. Herein, we report the first work to use cationic Gemini surfactants as modifiers to boost CO2 electroreduction to formate. The selectivity, activity and stability of the catalysts can be all significantly enhanced by Gemini surfactant modification. The Faradaic efficiency (FE) of formate could reach up to 96 %, and the energy efficiency (EE) could achieve 71 % over the Gemini surfactants modified Cu electrode. In addition, the Gemini surfactants modified commercial Bi2 O3 nanosheets also showed an excellent catalytic performance, and the FE of formate reached 91 % with a current density of 510 mA cm-2 using the flow cell. Detailed studies demonstrated that the double quaternary ammonium cations and alkyl chains of the Gemini surfactants played a crucial role in boosting electroreduction CO2 , which can not only stabilize the key intermediate HCOO* but also provide an easy access for CO2 . These observations could shine light on the rational design of organic modifiers for promoted CO2 electroreduction.

Quantitative Measurement of Drug Release Dynamics within Targeted Organelles Using Förster Resonance Energy Transfer.

Measuring the release dynamics of drug molecules after their delivery to the target organelle is critical to improve therapeutic efficacy and reduce side effects. However, it remains challenging to quantitatively monitor subcellular drug release in real time. To address the knowledge gap, a novel gemini fluorescent surfactant capable of forming mitochondria-targeted and redox-responsive nanocarriers is designed. A quantitative Förster resonance energy transfer (FRET) platform is fabricated using this mitochondria-anchored fluorescent nanocarrier as a FRET donor and fluorescent drugs as a FRET acceptor. The FRET platform enables real-time measurement of drug release from organelle-targeted nanocarriers. Moreover, the obtained drug release dynamics can evaluate the duration of drug release at the subcellular level, which established a new quantitative method for organelle-targeted drug release. This quantitative FRET platform can compensate for the absent assessment of the targeted release performances of nanocarriers, offering in-depth understanding of the drug release behaviors at the subcellular targets.

Preparation of Cubosomes with Improved Colloidal and Structural Stability Using a Gemini Surfactant.

Cubosomes are nanoparticles with bicontinuous cubic internal nanostructures that have been considered for use in drug delivery systems (DDS). However, their low structural stability is a crucial concern for medical applications. Herein, we investigated the use of a gemini surfactant, sodium dilauramidoglutamide lysine (DLGL), which is composed of two monomeric surfactants linked with a spacer to improve the structural stability of cubosomes prepared with phytantriol (PHY). Uniform nanosuspensions comprising a specific mixing ratio of DLGL and PHY in water prepared via ultrasonication were confirmed by using dynamic light scattering. Small-angle X-ray scattering and cryo-transmission electron microscopy revealed the formation of Pn3̅m cubosomes in a range of DLGL/PHY solid ratios between 1 and 3% w/w. By contrast, cubosome formation was not observed at DLGL/PHY solid ratios of 5% w/w or higher, suggesting that excess DLGL interfered with cubosome formation and caused them to transform into small unilamellar vesicles. The addition of phosphate-buffered saline to the nanosuspension caused aggregation when the solid ratio of DLGL/PHY was less than 5% w/w. However, Im3̅m cubosomes were obtained at solid ratios of DLGL/PHY of 6, 7.5, and 10% w/w. The lattice parameters of the Pn3̅m and Im3̅m cubosomes were approximately 7 and 11-13 nm, respectively. The lattice parameters of Im3̅m cubosomes were affected by the concentration of DLGL. Pn3̅m cubosomes were surprisingly stable for 4 weeks at both 25 and 5 °C. In conclusion, DLGL, a gemini surfactant, was found to act as a new stabilizer for PHY cubosomes at specific concentrations. Cubosomes composed of DLGL are stable under low-temperature storage conditions, such as in refrigerators, making them a viable option for heat-sensitive DDS.

Evaluation of the antiviral potential of gemini surfactants against influenza virus H1N1.

Influenza A virus (IAV) affects human health worldwide as a high-risk disease. It can neither be easily controlled by current vaccines and nor be treated by conventional drugs. Gemini surfactants (GS) have shown several properties including antiviral activity. In this study, the antiviral capacity of some GS compounds with different levels of hydrophobicity was examined. The 50% cytotoxic (CC50) and non-cytotoxic (NCTC) concentrations of the compounds were determined by MTT method. The NCTCs, the same as effective concentrations (EC50s), were tested for the antiviral capacity against IAV in different combination treatments for 1 h incubation on MDCK cells. The HA and MTT assays were used to evaluate the virus titer and cell viabilities, respectively. The hemolytic activity of the compounds was also assessed using an HA inhibition assay. To evaluate the apoptotic effect of GS compounds, Annexin V-PI kit was used. The HA titers decreased between 1-6.5 logs, 1-4.5 logs, and 1-5.5 logs in simultaneous, pre- and post-penetration combination treatments, respectively. The cell viability values in all combination treatments were favorable. The HI assay indicated the hemolytic potential of GSs and their physical interaction with viral HA. The apoptosis test results highlighted anti-apoptotic capacity of the GS compounds alone and in the presence of influenza virus especially for the hydrophobic ones. Gemini surfactants were generally more efficacious in simultaneous treatment. Their antiviral potential may be attributed to their physical interaction with viral membrane or HA glycoprotein that disrupts viral particle or blocks viral entry to the cell and inhibits its propagation.

Synthesis, Properties, and Biomedical Application of Dicationic Gemini Surfactants with Dodecane Spacer and Carbamate Fragments.

A synthesis procedure and aggregation properties of a new homologous series of dicationic gemini surfactants with a dodecane spacer and two carbamate fragments (N,N'-dialkyl-N,N'-bis(2-(ethylcarbamoyloxy)ethyl)-N,N'-dimethyldodecan-1,6-diammonium dibromide, n-12-n(Et), where n = 10, 12, 14) were comprehensively described. The critical micelle concentrations of gemini surfactants were obtained using tensiometry, conductometry, spectrophotometry, and fluorimetry. The thermodynamic parameters of adsorption and micellization, i.e., maximum surface excess (Гmax), the surface area per surfactant molecule (Amin), degree of counterion binding (ß), and Gibbs free energy of micellization (∆Gmic), were calculated. Functional activity of the surfactants, including the solubilizing capacity toward Orange OT and indomethacin, incorporation into the lipid bilayer, minimum inhibitory concentration, and minimum bactericidal and fungicidal concentrations, was determined. Synthesized gemini surfactants were further used for the modification of liposomes dual-loaded with α-tocopherol and donepezil hydrochloride for intranasal treatment of Alzheimer's disease. The obtained liposomes have high stability (more than 5 months), a significant positive charge (approximately + 40 mV), and a high degree of encapsulation efficiency toward rhodamine B, α-tocopherol, and donepezil hydrochloride. Korsmeyer-Peppas, Higuchi, and first-order kinetic models were used to process the in vitro release curves of donepezil hydrochloride. Intranasal administration of liposomes loaded with α-tocopherol and donepezil hydrochloride for 21 days prevented memory impairment and decreased the number of Aß plaques by 37.6%, 40.5%, and 72.6% in the entorhinal cortex, DG, and CA1 areas of the hippocampus of the brain of transgenic mice with Alzheimer's disease model (APP/PS1) compared with untreated animals.

Organo-Montmorillonite Modified by Gemini Quaternary Ammonium Surfactants with Different Counterions for Adsorption toward Phenol.

The discharge of industrial phenol pollutants causes great harm to the natural environment and human health. In this study, phenol removal from water was studied via the adsorption of Na-montmorillonite (Na-Mt) modified by a series of Gemini quaternary ammonium surfactants with different counterions [(C11H23CONH(CH2)2N+ (CH3)2(CH2)2 N+(CH3)2 (CH2)2NHCOC11H23·2Y-, Y = CH3CO3-, C6H5COO- and Br-, 12-2-12·2Y-]. The results of the phenol adsorption indicated that MMt-12-2-12·2Br-, MMt-12-2-12·2CH3CO3- and MMt-12-2-12·2C6H5COO- reached the optimum adsorption capacity, which was 115.110 mg/g, 100.834 mg/g and 99.985 mg/g, respectively, under the conditions of the saturated intercalation concentration at 2.0 times that of the cation exchange capacity (CEC) of the original Na-Mt, 0.04 g of adsorbent and a pH = 10. The adsorption kinetics of all adsorption processes were in good agreement with the pseudo-second-order kinetics model, and the adsorption isotherm was better modeled by Freundlich isotherm. Thermodynamic parameters revealed that the adsorption of phenol was a physical, spontaneous and exothermic process. The results also showed that the counterions of the surfactant had a certain influence on the adsorption performance of MMt for phenol, especially the rigid structure, hydrophobicity, and hydration of the counterions.

Self-Aggregation, Antimicrobial Activity and Cytotoxicity of Ester-Bonded Gemini Quaternary Ammonium Salts: The Role of the Spacer.

Five ester-bonded gemini quaternary ammonium surfactants C12-En-C12 (n = 2, 4, 6), with a flexible spacer group, and C12-Bm-C12 (m = 1, 2), with rigid benzene spacers, were synthesized via a two-step reaction and analyzed. Furthermore, the effects of the spacer structure, spacer length and polymerization degree on the self-aggregation, antimicrobial activity and cytotoxicity of C12-En-C12 and C12-Bm-C12 and their corresponding monomer N-dodecyl-N,N,N-trimethyl ammonium chloride DTAC were investigated. The results showed that C12-En-C12 and C12-Bm-C12 had markedly lower critical micellar concentration (CMC) values and lower surface tension than DTAC. Moreover, the CMC values of C12-En-C12 and C12-Bm-C12 decreased with increasing spacer length. In the case of equivalent chain length, the rigidity and steric hindrance of phenylene and 1,4-benzenediyl resulted in larger CMC values for C12-Bm-C12 than for C12-En-C12. The antibacterial ability of C12-En-C12 and C12-Bm-C12 was assessed using Escherichia coli (E. coli) and Staphylococcus albus (S. aureus) based on minimum inhibitory concentrations (MICs). Furthermore, C12-En-C12 and C12-Bm-C12 exhibited higher antimicrobial activity than DTAC and had stronger function toward S. aureus than E. coli. The antimicrobial activity was enhanced by increasing the spacer chain length and decreased with the increased rigidity of the spacers. The cytotoxic effects of C12-En-C12 and C12-Bm-C12 in cultured Hela cells were evaluated by the standard CCK8 method based on half-maximal inhibitory concentration (IC50). The cytotoxicity of C12-En-C12 and C12-Bm-C12 was significantly lower than alkanediyl-α,ω-bis(dimethyldodecylammonium) bromide surfactants and DTAC. The spacer structure and the spacer length could induce significant cytotoxic effects on Hela cells. These findings indicate that the five ester-bonded GQASs have stronger antibacterial activity and lower toxicity profile, and thus can be used in the pharmaceutical industry.

Peptide-Modified Gemini Surfactants as Delivery System Building Blocks with Dual Functionalities for Glaucoma Treatment: Gene Carriers and Amyloid-Beta (Aß) Self-Aggregation Inhibitors.

Retinal ganglion cell (RGC) neurodegeneration in glaucoma has potential links with amyloid-ß (Aß) deposition. Targeting the Aß pathway was shown to reduce RGC apoptosis and protect RGCs from degeneration. We report exploratory studies on the amyloid Aß40 aggregation inhibition properties of four cell adhesion peptide (CAP)-gemini surfactants that are intended as building blocks for gene carrier nanoparticles for glaucoma treatment. The CAP-gemini surfactants (18-7N(p1-4)-18) were evaluated as potential Aß40 peptide aggregation inhibitors by a fluorescence kinetic assay and for their binding interactions with Aß40 dimers by molecular docking studies. In vitro Aß40 peptide aggregation inhibition studies showed that the 18-7N(p3)-18 and 18-7N(p1)-18 ligands inhibit Aß40 peptide aggregation and prevent the formation of higher order structures. CDOCKER energies and CDOCKER interaction energies demonstrated that the CAP-gemini surfactants formed more stable complexes in the Aß40 dimer assembly and underwent both polar and nonpolar interactions compared to CAP peptides alone. Also, 18-7N(p3)-18 showed a significantly lower CDOCKER energy compared to that of the unmodified gemini surfactant 18-7NH-18 (p < 0.0001) and 18-7N(p4)-18 (p < 0.001), 18-7N(p1)-18, and 18-7N(p2)-18. Similarly, 18-7N(p3)-18 showed a significantly lower CDOCKER interaction energy compared to that of 18-7NH-18, 18-7N(p4)-18 (p < 0.0001), and 18-7N(p2)-18 (p < 0.001), while 18-7N(p3)-18 and 18-7N(p1)-18 showed similar CDOCKER interaction energies. These studies suggest that a combination of both hydrophobic and electrostatic interactions contributes to the anti-Aß40 aggregation activity of CAP-gemini surfactants. CAP-gemini surfactants showed 10-fold better Aß40 peptide aggregation inhibition compared to previously reported values and could provide a new opportunity for glaucoma treatment as dual-functional gene carriers.

Nanoformulation of Polyphenol Curcumin Enhances Cisplatin-Induced Apoptosis in Drug-Resistant MDA-MB-231 Breast Cancer Cells.

Triple Negative Breast Cancer (TNBC) is the aggressive and lethal type of breast malignancy that develops resistance to current therapies. Combination therapy has proven to be an effective strategy on TNBC. We aimed to study whether the nano-formulation of polyphenolic curcumin (Gemini-Cur) would affect the cisplatin-induced toxicity in MDA-MB-231 breast cancer cells. MDA-MB-231 cells were treated with Gemini-Cur, cisplatin and combination of Gemini-Cur/Cisplatin in a time- and dose-dependent manner. Cell viability was studied by using MTT, fluorescence microscopy and cell cycle assays. The mode of death was also determined by Hoechst staining and annexin V-FITC. Real-time PCR and western blotting were employed to detect the expression of BAX and BCL-2 genes. Our data demonstrated that Gemini-Cur significantly sensitizes cancer cells to cisplatin (combination index ≤ 1) and decreases IC50 values in comparison with Gemini-cur or cisplatin. Further studies confirmed that Gemini-Cur/Cisplatin suppresses cancer cell growth through induction of apoptosis (p < 0.001). In conclusion, the data confirm the synergistic effect of polyphenolic curcumin on cisplatin toxicity and provide attractive strategy to attain its apoptotic effect on TNBC.

Modulating the Excited State Chirality of Dynamic Chemical Reactions in Chiral Micelles.

Chirality generation and transfer is not only of critical importance in resolving the origin of biological homochirality, but also is of great significance for exploring the chirality-related functionalities in nanomaterials and supramolecular systems. Although modulating the ground state chirality in chiral nanomaterials has been widely demonstrated, it remains a big challenge to steer the excited state chirality (circularly polarized luminescence, CPL). Herein, we present a kind of chiral spherical micelles constructed by chiral cationic gemini surfactants, whose surfaces and cavities could co-assemble with hydrophilic and hydrophobic emitters concurrently. Subsequently, the hydrophilic and hydrophobic emitters could be endowed with CPL activity in the aqueous phase. Additionally, the cavities of such micelles can be regarded as the powerful chiral confined space, which could effectively modulate the excited state chirality of dynamic chemical reactions, enabling color-adjustable CPL emission.

Label-free Fluorescence Turn on Trypsin Assay Based on Gemini Surfactant/heparin/Nile Red Supramolecular Assembly.

In this research, we designed a label-free fluorometric turn-on assay for trypsin and inhibitor screening, based on a spherical cationic gemini surfactant ethylene-bis (dodecyl dimethyl ammonium bromide) (EDAB)/heparin/Nile red (NR) supramolecular assembly system. The introduction of gemini surfactant EDAB as template greatly enhanced its salt resistance and resulted in the supramolecular assemblies with diameters ranging from 20 to 100 nm. The fluorometric assay for trypsin was performed by firstly disassembling with protamine (a heparin-binding protein) and then re-assembling through hydrolysis of protamine. The disassembly and reassembly of the system resulted in a turn-off first and then a turn-on behavior of the corresponding fluorescence. The overall processes were characterized by fluorescence spectra, TEM measurements and zeta potential tests. The detection level of this assembly system for trypsin was as low as 4.2 ng mL-1. Also, the EDAB/heparin/NR assembly could be used to screen the trypsin inhibitors. The assembly system was easily-fabricated and cost-effective, but also exhibited good salt tolerance in NaCl solution at the concentration of 0-500 mM. At last, the supramolecular assembly was successfully applied to detect trypsin in human urine, demonstrating its great potential on clinical diagnosis applications.

pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants.

Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(N-dodecyl-N-propanesulfonate sodium)-propane (C12C3C12(SO3)2) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C12C3C12(SO3)2 through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C12C3C12(SO3)2 molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C12C3C12(SO3)2 solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C12C3C12(SO3)2, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.

Dicationic Amino Substituted Gemini Surfactants and their Nanoplexes: Improved Synthesis and Characterization of Transfection Efficiency and Corneal Penetration In Vitro.

PURPOSE: To formulate and characterize nanoparticles from m-7NH-m gemini surfactants, synthesized by a new improved method, for non-invasive gene delivery including optimization of composition for transfection efficiency and corneal penetration. METHODS: A one-pot, solvent-free, DMAP-free method was developed for the synthesis of m-7NH-m (m = 12-18) gemini surfactant series. Lipoplexes (LPXs) and nanoplexes (NPXs) of gemini surfactant-plasmid DNA were formulated with and without DOPE helper lipid, respectively, at various charge ratios and characterized by dynamic light scattering and zeta potential measurements. Transfection efficiency, cellular toxicity, effect of DOPE and gene expression kinetic studies were carried out in A7 astrocytes by flow cytometry and confocal microscopy. Corneal penetration studies of 18-7NH-18 NPXs were carried out using 3D EpiCorneal® tissue model. RESULTS: The new synthesis method provides a two-fold improved yield and the production of a pure species of m-7NH-m without DMAP and trimeric m-7N(m)-m surfactants as impurities. Structure and purity was confirmed by ESI-MS, 1H NMR spectroscopy and surface tension measurements. Particle size of 199.80 ± 1.83 nm ± S.D. and a zeta potential value of +30.18 ± 1.17 mV ± S.D. was obtained for 18-7NH-18 5:1 ratio NPXs showed optimum transfection efficiency (10.97 ± 0.11%) and low toxicity (92.97 ± 0.57% viability) at the 48-h peak expression. Inclusion of DOPE at 1: 0.5 and 1:1 ratios to gemini surfactant reduced transfection efficiency and increased toxicity. Treatment of EpiCorneal® tissue model showed deep penetration of up to 100 µm with 18-7NH-18 NPXs. CONCLUSION: Overall, 18-7NH-18 NPXs are potential gene delivery systems for ophthalmic gene delivery and for further in vivo studies.

Hierarchical chirality expression of gemini surfactant aggregates via equilibrium between chiral nucleotide and nonchiral mono-anions.

The assembling behaviors of nonchiral dicationic amphiphilic molecules (gemini) in the presence of the mixture of chiral anionic nucleotides and nonchiral anions are investigated. We demonstrate that subtle balance of various physico-chemical parameters and the competition between chiral and nonchiral anions at the interface of gemini assemblies influences the expression of molecular chirality at the micrometer scale through the hierarchical molecular assembly.

Novel Treatment for Mitigating Condensate Bank Using a Newly Synthesized Gemini Surfactant.

Condensate accumulation in the vicinity of the gas well is known to curtail hydrocarbon production by up to 80%. Numerous approaches are being employed to mitigate condensate damage and improve gas productivity. Chemical treatment, gas recycling, and hydraulic fracturing are the most effective techniques for combatting the condensate bank. However, the gas injection technique showed temporary condensate recovery and limited improvement in gas productivity. Hydraulic fracturing is considered to be an expensive approach for treating condensate banking problems. In this study, a newly synthesized gemini surfactant (GS) was developed to prevent the formation of condensate blockage in the gas condensate reservoirs. Flushing the near-wellbore area with GS will change the rock wettability and thereby reduce the capillary forces holding the condensate due to the strong adsorption capacity of GS on the rock surface. In this study, several measurements were conducted to assess the performance of GS in mitigating the condensate bank including coreflood, relative permeability, phase behavior, and nuclear magnetic resonance (NMR) measurements. The results show that GS can reduce the capillary pressure by as much as 40%, increase the condensate mobility by more than 80%, and thereby mitigate the condensate bank by up to 84%. Phase behavior measurements indicate that adding GS to the oil-brine system could not induce any emulsions at different salinity levels. Moreover, NMR and permeability measurements reveal that the gemini surfactant has no effect on the pore system and no changes were observed in the T2 relaxation profiles with and without the GS injection. Ultimately, this work introduces a novel and effective treatment for mitigating the condensate bank. The new treatment showed an attractive performance in reducing liquid saturation and increasing the condensate relative permeability.

Multiple Applications of a Novel Cationic Gemini Surfactant: Anti-Microbial, Anti-Biofilm, Biocide, Salinity Corrosion Inhibitor, and Biofilm Dispersion (Part II).

The Egyptian petroleum industries are incurring severe problems with corrosion, particularly corrosion that is induced by sulfidogenic microbial activities in harsh salinity environments despite extensively using biocides and metal corrosion inhibitors. Therefore, in this study, a synthesized cationic gemini surfactant (SCGS) was tested as a broad-spectrum antimicrobial, anti-bacterial, anti-candida, anti-fungal, anti-biofilm (anti-adhesive), and bio-dispersion agent. The SCGS was evaluated as a biocide against environmental sulfidogenic-bacteria and as a corrosion inhibitor for a high salinity cultivated medium. The SCGS displayed wide spectrum antimicrobial activity with minimum bactericidal/fungicidal inhibitory concentrations. The SCGS demonstrated anti-bacterial, anti-biofilm, and bio-dispersion activity. The SCGS exhibited bactericidal activity against environmental sulfidogenic bacteria and the highest corrosion inhibition efficiency of 93.8% at 5 mM. Additionally, the SCGS demonstrated bio-dispersion activity against the environmental sulfidogenic bacteria at 5.49% salinity. In conclusion, this study provides a novel synthesized cationic surfactant with many applications in the oil and gas industry: as broad-spectrum antimicrobial and anti-biofilm agents, corrosion inhibition for high salinity, biocides for environmentally sulfidogenic bacteria, and as bio-dispersion agents.

Dirhamnolipid ester - formation of reverse wormlike micelles in a binary (primerless) system.

We report new dirhamnolipid ester forming reverse wormlike micelles in nonpolar solvents without the addition of any primer. Therefore, these compounds represent a rare case of a binary system showing this gel-like behavior. In this study, the influence of the concentration of the rhamnolipid ester and the ester alkyl chain length on the rheological properties of the reverse wormlike micelles in toluene was investigated in detail. Highly viscoelastic solutions were obtained even at a relatively low concentration of less than 1 wt %. The phase transition temperatures indicate that the formation of reverse wormlike micelles is favored for dirhamnolipid esters with shorter alkyl chain lengths. Oscillatory shear measurements for the viscoelastic samples reveal that the storage modulus (G') and the loss modulus (G'') cross each other and fit the Maxwell model very well in the low-ω region. As is typical for wormlike micelle systems, the normalized Cole-Cole plot of G''/G'' max against G'/G'' max was obtained as a semicircle centered at G'/G'' max = 1. The formation of network structures was also verified by polarized light microscopy. The sample was birefringent at ambient temperature and anisotropic at an elevated temperature. Differential scanning calorimetry analysis yielded a transition enthalpy of about ΔH SG/GS = ±7.2 kJ/mol. This value corresponds to a strong dispersion energy and explains the formation of the highly viscous gels by the entanglement of wormlike micelles through the interaction of the alkyl chains.