Electrodeposition is an electrochemical method employed to deposit stable and robust gold nanoparticles (AuNPs) on electrode surfaces for creating chemically modified electrodes (CMEs). The use of several electrodeposition techniques with different experimental parameters allow in obtaining various surface morphologies of AuNPs deposited on the electrode surface. By considering the electrodeposition of AuNPs in various background electrolytes could play an important strategy in finding the most suitable formation of the electrodeposited AuNP films on the electrode surface. This is because different electrode roughnesses can have different effects on the electrochemical activities of the modified electrodes. Thus, in this study, the electrodeposition of AuNPs onto the glassy carbon (GC) electrode surfaces in various aqueous neutral and acidic electrolytes was achieved by using the cyclic voltammetry (CV) technique with no adjustable CV parameters. Then, surface morphologies and electrochemical activities of the electrodeposited AuNPs were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), CV, and electrochemical impedance spectroscopy (EIS). The obtained SEM and 3D-AFM images show that AuNPs deposited at the GC electrode prepared in NaNO3 solution form a significantly better, uniform, and homogeneous electrodeposited AuNP film on the GC electrode surface with nanoparticle sizes ranging from ∼36 to 60 nm. Meanwhile, from the electrochemical performances of the AuNP-modified GC electrodes, characterized by using a mixture of ferricyanide and ferrocyanide ions [Fe(CN6)3-/4-], there is no significant difference observed in the case of charge-transfer resistances (R ct) and heterogeneous electron-transfer rate constants (k o), although there are differences in the surface morphologies of the electrodeposited AuNP films. Remarkably, the R ct values of the AuNP-modified GC electrodes are lower than those of the bare GC electrode by 18-fold, as the R ct values were found to be ∼6 Ω (p < 0.001, n = 3). This has resulted in obtaining k o values of AuNP-modified GC electrodes between the magnitude of 10-2 and 10-3 cm s-1, giving a faster electron-transfer rate than that of the bare GC electrode (10-4 cm s-1). This study confirms that using an appropriate supporting background electrolyte plays a critical role in preparing electrodeposited AuNP films. This approach could lead to nanostructures with a more densely, uniformly, and homogeneously electrodeposited AuNP film on the electrode surfaces, albeit utilizing an easy and simple preparation method.
A short, asymmetric synthesis of tetrahydro-2H-furo[3,2-b]pyrrole derivatives and (-)-Geissman-Waiss lactone starting from meso-cyclohexadiene epoxide is described. Pivotal transformations in the developed synthetic procedure include asymmetric epoxide ring opening to install the requisite 1S,5S stereocenters and oxidative lactonization/lactamization sequences. This route provides a streamlined synthetic pathway toward necine alkaloids.
Aripiprazole (ARP), a quinolinone derivative, is an atypical antipsychotic drug that is used in the treatment of schizophrenia. ARP has an extensive distribution and more than 99% of the ARP and dehydro-ARP, the main active metabolite, is bound to plasma proteins. However, information regarding the protein binding of ARP is limited. In this study, we report on a systematic study of the protein binding of ARP. The interaction of ARP and structurally related compounds with human serum albumin (HSA) was examined using equilibrium dialysis, circular dichroism (CD) spectroscopy, fluorescent probe displacement, and an X-ray crystallographic analysis. The binding affinities (nK) for ARP and its main metabolite, dehydro-ARP with HSA were found to be significantly higher than other structurally related compounds. The results of equilibrium dialysis experiments and CD spectral data indicated that the chloro-group linked to the phenylpiperazine ring in the ARP molecule plays a major role in the binding of these ligands to HSA. Furthermore, fluorescent probe displacement results indicated that ARP appears to bind at the site II pocket in subdomain III. A detailed CD spectral analysis suggests that the chloro-group linked to the phenylpiperazine ring may control the geometry of the ARP molecule when binding in the site II binding pocket. X-ray crystallographic analysis of the ARP-HSA complex revealed that the distance between the chlorine atom at the 3-positon of dichlorophenyl-piperazine on ARP and the sulfur atom of Cys392 in HSA was 3.4-3.6 Å. A similar halogen bond interaction has also been observed in the HSA structure complexed with diazepam, which also contains a chloro-group. Thus, the mechanism responsible for the binding of ARP to a protein elucidated here should be relevant for assessing the pharmacokinetics and pharmacodynamics of ARP in various clinical situations and for designing new drugs.
Aiming for glycolipid-based vesicles for targeted drug delivery, cationic Guerbet glycosides with spacered click functionality were designed and synthesized. The cationic charge promoted the distribution of the glycolipids during the formulation, thereby leading to homogeneously small vesicles. The positive surface charge of the vesicles stabilizes them against unwanted fusion and promotes interactions of the drug carriers with typical negative charge-dominated target cells. High bioconjugation potential of the functionalized glycolipids based on the copper-catalyzed azide alkyne cycloaddition makes them highly valuable components for targeted drug delivery systems.
This study aims at investigating the distortion of poly(dimethylsiloxane) (PDMS) nanostructures in a soft lithography demolding process using molecular dynamics simulation. Experimental results show that after peeling, PDMS nanopillars became 10-60% longer in height than the mold size. Molecular dynamics simulations have been employed to plot the stress-strain curve of the nanopillars when subjected to uniaxial stress. Three force fields (COMPASS, CVFF, and PCFF) were used for modeling. The demolding process in soft lithography and nanoimprint lithography causes significant deformation in replication. The experimental results show clear signs of elongation after demolding. Molecular dynamics simulations are employed to study the stress-strain relationship of the PDMS nanopillars. The results from the simulation show that a PDMS nanopillar at temperature T = 300 K under tensile stress shows characteristics of flexible plastic under tensile stress and has a lower Young's modulus, ultimate tensile stress, and Poisson's ratio.
An increase of nucleate pool boiling with the use of different fluid properties has received much attention. In particular, the presence of nanostructures in fluids to enhance boiling was given special consideration. This study compares the effects of graphene nanoplatelet (GNP), functionalized GNP with polyethylene glycol (PEG), and multiwalled carbon nanotube (CNT) nanofluids on the pool boiling heat transfer coefficient and the critical heat flux (CHF). Our findings showed that at the same concentration, CHF for functionalized GNP with PEG (GNP-PEG)/deionized water (DW) nanofluids was higher in comparison with GNP- and CNT-based nanofluids. The CHF of the GNP/DW nanofluids was also higher than that of CNT/DW nanofluids. The CHF of GNP-PEG was 72% greater than that of DW at the concentration of 0.1 wt %. There is good agreement between measured critical heat fluxes and the Kandlikar correlation. In addition, the current results proved that the GNP-PEG/DW nanofluids are highly stable over 3 months at a concentration of 0.1 wt %.
The application of graphene in the field of drug delivery has attracted massive interest among researchers. However, the high toxicity of graphene has been a drawback for its use in drug delivery. Therefore, to enhance the biocompatibility of graphene, a new route was developed using ternary natural deep eutectic solvents (DESs) as functionalizing agents, which have the capability to incorporate various functional groups and surface modifications. Physicochemical characterization analyses, including field emission scanning electron microscope, fourier-transform infrared spectroscopy, Raman spectroscopy, Brunauer-Emmett-Teller, X-ray diffraction, and energy dispersive X-ray, were used to verify the surface modifications introduced by the functionalization process. Doxorubicin was loaded onto the DES-functionalized graphene. The results exhibited significantly improved drug entrapment efficiency (EE) and drug loading capacity (DLC) compared with pristine graphene and oxidized graphene. Compared with unfunctionalized graphene, functionalization with DES choline chloride (ChCl):sucrose:water (4:1:4) resulted in the highest drug loading capacity (EE of 51.84% and DLC of 25.92%) followed by DES ChCl:glycerol:water (1:2:1) (EE of 51.04% and DLC of 25.52%). Following doxorubicin loading, graphene damaged human breast cancer cell line (MCF-7) through the generation of intracellular reactive oxygen species (>95%) and cell cycle disruption by increase in the cell population at S phase and G2/M phase. Thus, DESs represent promising green functionalizing agents for nanodrug carriers. To the best of our knowledge, this is the first time that DES-functionalized graphene has been used as a nanocarrier for doxorubicin, illustrating the potential application of DESs as functionalizing agents in drug delivery systems.
Superparamagnetic nanoparticles (SPNs) have been considered as one of the most studied nanomaterials for subsurface applications, including in enhanced oil recovery (EOR), due to their unique physicochemical properties. However, a comprehensive understanding of the effect of surface functionalization on the ability of the nanoparticles to improve secondary and tertiary oil recoveries remains unclear. Therefore, investigations on the application of bare and surface-functionalized SPNs in EOR using a sand pack were carried out in this study. Here, the as-prepared SPNs were functionalized using oleic acid (OA) and polyacrylamide (PAM) to obtain several types of nanostructure architectures such as OA-SPN, core-shell SPN@PAM, and SPN-PAM. Based on the result, it is found that both the viscosity and mobility of the nanofluids were significantly affected by not only the concentration of the nanoparticles but also the type and architecture of the surface modifier, which dictated particle hydrophilicity. According to the sand pack tests, the nanofluid containing SPN-PAM was able to recover as much as 19.28% of additional oil in a relatively low concentration (0.9% w/v). The high oil recovery enhancement was presumably due to the ability of suspended SPN-PAM to act as a mobility control and wettability alteration agent and facilitate the formation of a Pickering emulsion and disjoining pressure.
The present study examines the effect of human monoamine oxidase active anthraquinones emodin, alaternin (=7-hydroxyemodin), aloe-emodin, and questin from Cassia obtusifolia Linn seeds in modulating human dopamine (hD1R, hD3R, and hD4R), serotonin (h5-HT1AR), and vasopressin (hV1AR) receptors that were predicted as prime targets from proteocheminformatics modeling via in vitro cell-based functional assays, and explores the possible mechanisms of action via in silico modeling. Emodin and alaternin showed a concentration-dependent agonist effect on hD3R with EC50 values of 21.85 ± 2.66 and 56.85 ± 4.59 μM, respectively. On hV1AR, emodin and alaternin showed an antagonist effect with IC50 values of 10.25 ± 1.97 and 11.51 ± 1.08 μM, respectively. Interestingly, questin and aloe-emodin did not have any observable effect on hV1AR. Only alaternin was effective in antagonizing h5-HT1AR (IC50: 84.23 ± 4.12 μM). In silico studies revealed that a hydroxyl group at C1, C3, and C8 and a methyl group at C6 of anthraquinone structure are essential for hD3R agonist and hV1AR antagonist effects, as well as for the H-bond interaction of 1-OH group with Ser192 at a proximity of 2.0 Å. Thus, based on in silico and in vitro results, hV1AR, hD3R, and h5-HT1AR appear to be prime targets of the tested anthraquinones.
The manifestation of class D β-lactamases in the community raises significant concern as they can hydrolyze carbapenem antibiotics. Hence, it is exceptionally alluring to design novel inhibitors. Structure-based virtual screening using docking programs and molecular dynamics simulations was employed to identify two novel non-β-lactam compounds that possess the ability to block different OXA variants. Furthermore, the presence of a nonpolar aliphatic amino acid, valine, near the active site serine, was identified in all OXA variants that can be accounted to block the catalytic activity of OXA enzymes.
The reinforcing silica filler, which can be more than 40% of an elastomer composite, plays a key role to achieve the desired mechanical properties in elastomer vulcanizates. However, the highly hydrophilic nature of silica surface causes silica particle aggregation. It remained a challenge for many tire manufacturers when using silica-filled elastomer compounds. Here, the silica surface energy changes when the surface is modified with coupling or noncoupling silanes; coupling silanes can covalently bond the silica to the elastomers. The surface energy of silica was determined using inverse gas chromatography (IGC) at finite dilution (FD-IGC) and found to be reduced by up to 50% when the silica surface was silanized. The spatial distribution of silica aggregates within the tire matrix is determined by transmission electron microscopy (TEM) and a direct correlation between aggregate size (silica microdispersion) and work of cohesion from IGC is reported, highlighting surface energy and work of cohesion being excellent indicators of the degree of dispersion of silica aggregates.
Synthesis of a series of benzimidazole-ornamented pyrazoles, 6a-6j has been obtained from arylhydrazine and aralkyl ketones via a multistep synthetic strategy. Among them, a hybrid-possessing para-nitrophenyl moiety connected to a pyrazole scaffold (6a) exerted the highest anti-inflammatory activity, which is superior to the standard, diclofenac sodium. While executing the 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity, a hybrid-possessing para-bromophenyl unit integrated at the pyrazole structural motif (6i) exhibited the highest activity among the hybrids examined. Besides, evaluation of anticancer potency of the synthesized hybrids revealed that the one containing a para-fluorophenyl unit tethered at the pyrazole nucleus (6h) showed the highest activity against both the pancreatic cancer cells (SW1990 and AsPCl) investigated. Considerable binding affinity between B-cell lymphoma and the hybrid, 6h has been reflected while performing molecular docking studies (-8.65 kcal/mol). The outcomes of the investigation expose that these hybrids could be used as effective intermediates to construct more potent biological agents.
A mild and effective synthesis of resorcinol-furfural (RF) thermosetting resin was proposed with ethanol as a distinctive solvent, which, as a usually neglected factor, was shown to not only help form a homogeneous reaction system but also observably reduce the energy barriers between the early intermediates and transition states in addition reactions by explicit solvent effects, drawn from theoretical calculation conclusions. Besides, the para-additions on aromatic rings were more dominant than ortho-additions with the same reactants, which affected the final link types of monomers verified by Fourier transform infrared spectroscopy and two-dimensional nuclear magnetic resonance tests. The prepared resin can be assigned to a relatively fast gel speed and a high residual mass (65.25%) after pyrolysis in a N2 atmosphere by adjusting the molar ratios of F to R, and the curing of that was a complex reaction, with a curing temperature around 149 °C and an activation energy of about 49.11 kJ mol-1 obtained by the Kissinger method.
The discharge of industrial effluents, such as phenol, into aquatic and soil environments is a global problem due to its serious negative impacts on human health and aquatic ecosystems. In this study, the ability of polyvinylpolypyrrolidone (PVPP) to remove phenol from an aqueous medium was investigated. The results showed that a significant proportion of phenol (up to 74.91%) was removed using PVPP at pH 6.5. Isotherm adsorption experiments of phenol on PVPP indicated that the best-fit adsorption was obtained using Langmuir models. The response peaks of the hydroxyl groups of phenol (OH) and the carboxyl groups (i.e., C=O) of PVPP were altered, indicating the formation of a hydrogen bond between the PVPP and phenol during phenol removal, as characterized using 1D and 2D IR spectroscopy. The resulting complexes were successfully characterized based on their thermodynamic properties, Mulliken charge, and electronic transition using the DFT approach. To clarify the types of interactions taking place in the complex systems, quantum theory of atoms in molecules (QTAIM) analysis, reduced density gradient noncovalent interaction (RDG-NCI) approach, and conductor-like screening model for real solvents (COSMO-RS) approach were also successfully calculated. The results showed that the interactions that occurred in the process of removing phenol by PVPP were through hydrogen bonding (based on RDG-NCI and COSMO-RS), which was identified as an intermediate type (∇2ρ(r) > 0 and H < 0, QTAIM). To gain a deeper understanding of how these interactions occurred, further characterization was performed based on adsorption mechanisms using molecular electrostatic potential, global reactivity, and local reactivity descriptors. The results showed that during hydrogen bond formation, PVPP acts as a nucleophile, whereas phenol acts as an electrophile and the O9 atom (i.e., donor electron) reacts with the H22 atom (i.e., acceptor electron).
Membrane distillation (MD) is a thermal technology for the desalination process that requires a hydrophobic microporous membrane to ensure that the membrane can maintain the liquid-vapor interface. This work aims to enhance the water permeation flux of the previously coated membrane by modifying the surface of the polytetrafluoroethylene hollow fiber (PTFE HF) membrane with a selected non-solvent such as acetone, cyclohexanone, and ethanol in low-density polyethylene as a polymeric coating solution. However, the modification using acetone and cyclohexanone solvents was unsuccessful because a reduction in membrane hydrophobicity was observed. The modified PTFE HF membrane with ethanol content exhibits high wetting resistance with a high water contact angle, which can withstand pore wetting during the direct contact MD process. Since MD operates under a lower operating temperature range (50-90 °C) compared to the conventional distillation, we herein demonstrated that higher flux could be obtained at 7.26 L m-2 h-1. Thus, the process is economically feasible because of lower energy consumption. Performance evaluation of the modified PTFE HF membrane showed a high rejection of 99.69% for sodium chloride (NaCl), indicating that the coated membrane preferentially allowed only water vapor to pass through.
Coral-like and nanowire (NW) iron oxide nanostructures were produced at 700 and 800 °C, respectively, through thermal oxidation of iron foils in air- and water vapor-assisted conditions. Water vapor-assisted thermal oxidation at 800 °C for 2 h resulted in the formation of highly crystalline α-Fe2O3 NWs with good foil surface coverage, and we propose that their formation was due to a stress-driven surface diffusion mechanism. The Cr(VI) adsorption property of an aqueous solution on α-Fe2O3 NWs was also evaluated after a contact time of 90 min. The NWs had a removal efficiency of 97% in a 225 mg/L Cr(VI) solution (pH 2, 25 °C). The kinetic characteristic of the adsorption was fitted to a pseudo-second-order kinetic model, and isothermal studies indicated that the α-Fe2O3 NWs exhibited an adsorption capacity of 66.26 mg/g. We also investigated and postulated a mechanism of the Cr(VI) adsorption in an aqueous solution of α-Fe2O3 NWs.
This work established a high-speed camera-assisted visualization system that investigated the effect of volatile matter and fixed carbon content in biomass particles on single-particle combustion phases and their luminous properties. Three types of biomass particles, namely, sawdust (a mixture of pine and willow), corncob, and rice husk, were examined on a Hencken flat-flame burner. The luminous region and intensity of single biomass particles were closely related to the flammability and calorific value of biomass fuel and derived by analyzing a sequence of images captured using a high-speed camera. The combustion temperature was determined through analysis of its radiant energy. The results showed that the ignition mechanisms of volatile matter and fixed carbon corresponded to homogeneous and heterogeneous reactions, respectively. The maximum luminous region values of 1.75 × 106, 2.1 × 106, and 1.0 × 106 μm2 for sawdust (SD), corncob (CC), and rice husk (RH) correlated to the volatile matter content of each biomass sample, which was 69.38, 74.15, and 64.56%, respectively. Because of the high fixed carbon content, the peak temperature of the SD particles could reach 1549 °C. The luminous region and intensity of the combusting particles were significantly affected by the volatile matter and fixed carbon, respectively.
This work presents a cost-effective approach for processing of renewable carbon-rich biomass using pyridinium-based Lewis acidic ionic liquids (LAILs). Rice husk as carbon-rich lignocellulosic waste was pretreated with a series of neutral and Lewis acidic ionic liquids to yield valuable intermediate platform monosaccharides. Novelty in the work lies in direct conversion of lignocellulosic carbohydrates into reducing sugars without their further conversion into 5-hydroxymethylfurfural or any other platform chemicals that are fermentation inhibitors for bioethanol production. The unconverted cellulose-rich material (CRM) is regenerated as a delignified material by the simultaneous addition of antisolvents. CRM and recovered lignin obtained after pretreatment were analyzed via scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) spectroscopy. The process was optimized with respect to a high yield of platform sugars and the quantity as well as quality of recovered CRM and lignin contents. Various reaction parameters involving the molecular structure of ionic liquids (ILs), Lewis acidic strength of ILs, biomass loading into IL, time, temperature, and biomass particle size were screened thoroughly. From all of the tested ILs, unsymmetrical 3-methylpyridinium IL having N-octyl substitution and chloroaluminate anion showed a greater conversion efficiency at 100 °C for 1.5 h. FTIR and SEM analyses of recovered CRM justify >90% lignin removal from rice husk. From all of the removed lignin, 60 wt % of original lignin content was recovered. The Lewis acidic system possessed recycling ability up to 3 times for subsequent treatment of rice husk without a significant loss of efficiency.
Antibacterial resistance remains a major global problem due to frequent prescriptions, leading to significant toxicities. To overcome the limitations of antibiotic therapy, it is highly desirable to provide site-specific delivery of drugs with controlled release. Inspired by the biocompatible, biodegradable, and site-specific mimicking behavior of poly(ethylene glycol) (PEG) and poly(caprolactone) (PCL), we developed vancomycin-PEG-PCL-PEG conjugates to maximize the pharmacological effects and minimize the side effects. Drug-loaded vancomycin-PEG-PCL-PEG conjugates are influenced by size, shape, surface area, encapsulation efficiency, in vitro drug release, hemolysis assay, cytotoxicity, and antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) and bacterial kill kinetics. The results demonstrated that vancomycin (VCM) release from PEG-PCL-PEG triblock revealed a biphasic manner. Hemolysis assay showed the nonprescription nature of VCM-PEG-PCL-PEG. Cytotoxicity studies confirmed the biocompatibility of VCM-PEG-PCL-PEG. The in vitro antibacterial results showed enhance activity with minimum inhibitory concentration compared to bare VCM. Molecular dynamics simulation study revealed that binding between VCM and PEG-PCL-PEG by hydrophobic interactions offers molecular encapsulation and steric barrier to drug degradation. This newly developed therapeutic delivery system can offer to enhance activity and delivery VCM against MRSA.
CO2 levels in the atmosphere are growing as a result of the burning of fossil fuels to meet energy demands. The introduction of chemical looping combustion (CLC) as an alternative to traditional combustion by transporting oxygen emphasizes the need to develop greener and more economical energy systems. Metal oxide, also defined as an oxygen carrier (OC), transports oxygen from the air to the fuel. Several attempts are being made to develop an OC with a reasonable material cost for superior fuel conversion and high oxygen transport capacity (OTC). This study aims to synthesize a potential OC using the wet impregnation method for the CLC process. Thermogravimetric analysis (TGA) was used to determine the cyclic redox properties using 5% CH4/N2 and air as reducing and oxidizing gases, respectively. The 10CuPA-based OC retained a high OTC of about 0.0267 mg O2/mg of OC for 10 cycles that was higher than 10CuA-based OC. Furthermore, the oxygen transfer rate for 10CuPA-based OC was relatively higher compared to 10CuA-based OC over 10 cycles. In comparison to 10CuA-based OC, the 10CuPA-based OC presented a steady X-ray diffraction (XRD) pattern after 10 redox cycles, implying that the phase was stably restored due to praseodymium-modified γ alumina support.