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Therapeutics for actively targeting over-expressed receptors are of great interest because the majority of diseased tissues originate from normal cells and do not possess a unique receptor from which they can be differentiated. One such receptor is CD44, which has been shown to be highly overexpressed in many breast cancers and other types of cancer cells. While CD44 has been documented to express low levels in normal adult neurons, astrocytes, and microglia, this receptor may be overexpressed by neuroblastoma and neuroglioma. If differential expression exists between normal and cancerous cells, hyaluronan (HA) could be a useful carrier that targets carcinomas. Thus, HA was conjugated with resveratrol (HA-R), and its efficacy was tested on cortical-neuroblastoma hybrid, neuroblastoma, and neuroglioma cells. Confocal and flow cytometry showed these cells express CD44 and are able to bind and uptake HA-R. The toxicity of HA-R correlated well with CD44 expression in this study. Therefore, conjugating resveratrol and other chemotherapeutics to HA could minimize the side effects for normal cells within the brain and nervous system and could be a viable strategy for developing targeted therapies.
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This study is designed to formulate and characterize chitosan-based nanogels that provide the controlled delivery of anesthetic drugs, such as bupivacaine (BPV), for effective postoperative pain management over prolonged periods of time. Drug carriers of chitosan/poly (MMA-co-HEMA-cl-EGDMA) (CsPMH) nanogels were prepared by varying the composition of comonomers such as MMA, HEMA, and redox initiator CAN. The nanogels were then characterized using FTIR, TGA, SEM, and TEM. The CsPMH nanogels showed greater encapsulation efficiencies from 43.20-91.77%. Computational studies were also conducted to evaluate the interaction between the drug and CsPMH nanoparticles. Finally, BPV-loaded nanoparticles were used to examine their in vitro release behavior. At pH 7.4, all the drug carriers displayed the "n" value around 0.7, thus the BPV release follows anomalous diffusion. Drug carrier 7 demonstrated a steady and sustained release of BPV for approximately 24 h and released about 91% of BPV, following the K-P mechanism of drug release. On the other hand, drug carrier 6 exhibited controlled release for approximately 12 h and released only 62% of BPV.
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Quitosano , Nanopartículas , Nanogeles , Quitosano/química , Bupivacaína , Portadores de Fármacos/química , Concentración de Iones de HidrógenoRESUMEN
The rapid development of communication networks (5G and 6G) that rely on high-speed devices requiring fast and high-quality intra- and inter-terminal signal transmission media has led to a steady increase in the need for high-performance, low-dielectric-constant (Dk) (<2.5) materials. Consequently, low-dielectric polymeric materials, particularly polyimides (PIs), are very attractive materials that are capable of meeting the requirements of high-performance terminal devices that transmit broadband high-frequency signals. However, such a PI needs to be properly designed with appropriate properties, including a low Dk, low dielectric loss (Df), and low water absorptivity. PI materials are broadly used in various fields owing to their superior property/processibility combinations. This review summarizes the structural designs of PIs with low Dk and Df values, low water-absorbing capacity, and high optical transparency intended for communication applications. Furthermore, we characterize structure-property relationships for various PI types and finally propose structural modifications required to obtain useful values of the abovementioned parameters.
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Graphene is a well-known two-dimensional material with a large surface area and is used for numerous applications in a variety of fields. Metal-free carbon materials such as graphene-based materials are widely used as an electrocatalyst for oxygen reduction reactions (ORRs). Recently, more attention has been paid to developing metal-free graphenes doped with heteroatoms such as N, S, and P as efficient electrocatalysts for ORR. In contrast, we found our prepared graphene from graphene oxide (GO) by the pyrolysis method under a nitrogen atmosphere at 900 °C has shown better ORR activity in aqueous 0.1 M potassium hydroxide solution electrolyte as compared with the electrocatalytic activity of pristine GO. At first, we prepared various graphene by pyrolysis of 50 mg and 100 mg of GO in one to three alumina boats and pyrolyzed the samples under a N2 atmosphere at 900 °C. The prepared samples are named G50-1B to 3B and G100-1B and G100-2B. The prepared GO and graphenes were also analyzed under various characterization techniques to confirm their morphology and structural integrity. The obtained results suggest that the ORR electrocatalytic activity of graphene may differ based on the pyrolysis conditions. We found that G100-1B (Eonset, E1/2, JL, and n values of 0.843, 0.774, 4.558, and 3.76) and G100-2B (Eonset, E1/2, and JL values of 0.837, 0.737, 4.544, and 3.41) displayed better electrocatalytic ORR activity, as did Pt/C electrode (Eonset, E1/2, and JL values of 0.965, 0.864, 5.222, and 3.71, respectively). These results display the wide use of the prepared graphene for ORR and also can be used for fuel cell and metal-air battery applications.
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This study examined the gel behavior of naturally-occurring palmyra palm kernel (PPK). Due to the presence of polysaccharide in PPK hydrogels, they exhibit excellent swelling behavior in response to pH. Chemotherapeutic drug 5-fluorouracil (5-FU) was encapsulated in these gels using an equilibrium swelling technique. It was found that 5-FU had an encapsulation efficiency of up to 62%. To demonstrate the drug stability in the gels, the PPK hydrogels were characterized using fourier transform infrared spectroscopy, differential scanning calorimetry, and X-ray diffraction. The results showed that the PPK hydrogel matrix contained molecularly dispersed 5-FU drug. The PPK hydrogel exhibited a denser structure and a rough surface, according to images obtained by scanning electron microscopy. In vitro release tests were carried out at pH 1.2 (gastric fluid) and 7.4 (intestinal fluid). The efficacy of the encapsulation and the release patterns were influenced by the network topology of the PPK hydrogel. The release patterns showed that 5-FU was released gradually over a time internal of more than 12 h. The findings suggest that naturally-occurring PPK hydrogels loaded with chemotherapeutic drugs could be employed to treat colon cancer.
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In this study, a novel MXene (Ti3C2Tx)-based nanocarrier was developed for drug delivery. MXene nanosheets were functionalized with 3, 3'-diselanediyldipropionic acid (DSeDPA), followed by grafting doxorubicin (DOX) as a model drug to the surface of functionalized MXene nanosheets (MXene-Se-DOX). The nanosheets were characterized using scanning electron microscopy, atomic force microscopy (AFM), transmission electron microscopy, energy-dispersive X-ray spectroscopy (EDX), nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and zeta potential techniques. The drug-loading capacity (17.95%) and encapsulation efficiency (41.66%) were determined using ultraviolet-visible spectroscopy. The lateral size and thickness of the MXene nanosheets measured using AFM were 200 nm and 1.5 nm, respectively. The drug release behavior of the MXene-Se-DOX nanosheets was evaluated under different medium conditions, and the nanosheets demonstrated outstanding dual (reactive oxygen species (ROS)- and pH-) responsive properties. Furthermore, the MXene-Se-DOX nanosheets exhibited excellent antibacterial activity against both Gram-negative E. coli and Gram-positive B. subtilis.
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Sistemas de Liberación de Medicamentos , Escherichia coli , Doxorrubicina/farmacología , Doxorrubicina/química , Antibacterianos/farmacología , Antibacterianos/química , Liberación de Fármacos , Espectroscopía Infrarroja por Transformada de Fourier , Concentración de Iones de HidrógenoRESUMEN
Premature drug release and poor controllability is a challenge in the practical application of tumor therapy, which may lead to poor chemotherapy efficacy and severe adverse effects. In this study, a reactive oxygen species (ROS)-cleavable nanoparticle system (MXene-TK-DOX@PDA) was designed for effective chemotherapy drug delivery and antibacterial applications. Doxorubicin (DOX) was conjugated to the surface of (3-aminopropyl)triethoxysilane (APTES)-functionalized MXene via an ROS-cleavable diacetoxyl thioketal (TK) linkage. Subsequently, the surfaces of the MXene nanosheets were coated with pH-responsive polydopamine (PDA) as a gatekeeper. PDA endowed the MXene-TK-DOX@PDA nanoparticles with superior biocompatibility and stability. The MXene-TK-DOX@PDA nanoparticles had an ultrathin planar structure and a small lateral size of approximately 180 nm. The as-synthesized nanoparticles demonstrated outstanding photothermal conversion efficiency, superior photothermal stability, and a remarkable extinction coefficient (23.3 L g-1 cm-1 at 808 nm). DOX exhibited both efficient ROS-responsive and pH-responsive release performance from MXene-TK-DOX@PDA nanoparticles due to the cleavage of the thioketal linker. In addition, MXene-TK-DOX@PDA nanoparticles displayed high antibacterial activity against both Gram-negative Escherichia coli (E. coli) and Gram-positive Bacillus subtilis (B. subtilis) within 5 h. Taken together, we hope that MXene-TK-DOX@PDA nanoparticles will enrich the drug delivery system and significantly expand their applications in the biomedical field.
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In this study, a novel diamine monomer containing ester and phenyl moieties, 1,2-diphenylethane-1,2-diyl bis(4-aminobenzoate) (1,2-DPEDBA), was synthesized through a three-step reaction. Using this diamine, a novel polyimide (PI) film was prepared with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6-FDA) as a counter dianhydride through a typical two-step chemical imidization. For comparison, poly(pyromellitic dianhydride-co-4,4'-oxydianiline) (PMDA-ODA PI) was also synthesized via thermal imidization. The resulting 6-FDA-DPEDBA PI film was not only soluble in common polar solvents with high boiling points, such as N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF), but also soluble in common low-boiling-point polar solvents, such as chloroform (CHCl3) and dichloromethane (CH2Cl2), at room temperature. The resulting novel PI showed a 5% weight loss temperature (T5d) at 360 °C under a nitrogen atmosphere. The resulting PI film was colorless and transparent with a transmittance of 87.1% in the visible light region ranging from 400 to 760 nm. The water absorption of the novel PI film was of 1.78%. The PI film also possessed a good moisture barrier and hydrophobicity. Furthermore, the resulting PI film displayed a low dielectric constant of 2.17 at 106 Hz at room temperature. In conclusion, the novel PI film exhibited much better optical transparency, lower moisture absorption, and a lower dielectric constant as well as better solubility than the PMDA-ODA PI film, which is insoluble in any solvent, although its thermal stability is not better than that of PMDA-ODA PI.
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In this work, polyacrylic acid-functionalized MCM-41 was synthesized, which was made to interact with calcium ions, in order to realize enhanced pH-responsive nanocarriers for sustained drug release. First, mesoporous silica nanoparticles (MSNs) were prepared by the sol-gel method. Afterward, a (3-trimethoxysilyl)propyl methacrylate (TMSPM) modified surface was prepared by using the post-grafting method, and then the polymerization of the acrylic acid was performed. After adding a calcium chloride solution, polyacrylic acid-functionalized MSNs with calcium-carboxyl ionic bonds in the polymeric layer, which can prevent the cargo from leaking out of the mesopore, were prepared. The structure and morphology of the modified nanoparticles (PAA-MSNs) were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), and N2 adsorption-desorption analysis, etc. The controlled release of guest molecules was studied by using 5-fluorouracil (5-FU). The drug molecule-incorporated nanoparticles showed different releasing rates under different pH conditions. It is considered that our current materials have the potential as pH-responsive nanocarriers in the field of medical treatment.
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The hierarchical halloysite nanotubes (HNT) have alumina containing positive Al-OH groups on its inner surface and silica-containing negative siloxane groups of Si-O-Si on its outer surface. The silicate laminate consists of silicon-oxygen at tetrahedral sites and aluminum-oxygen at octahedral sites. Since HNT has an abundant hydroxyl group on the surface with exceptional cation/anion exchange capacity, the surface-functionalized HNT could boost electrocatalytic activity. Hence, we have synthesized Ni, Co, and Cu metal oxy/hydroxides functionalized HNT by a facile hydrothermal method for HER. Among them, Co(OH)2@HNT on flexible carbon cloth displays an ultra-low overpotential of 65 mV at 10 mA cm-2 current density and Tafel slope of 181 mV dec-1 and also exhibited a larger exchange current density of 3.98 mA cm-2 in alkaline 1 M KOH electrolyte due to superior electrostatic affinity between OH- and Co2+. The electrolyzers with anion exchange membrane consisting of RuO2||Co(OH)2@HNT show remarkable stability of over 50 h at 10 mA cm-2 in alkaline electrolyte. The post stability sample retains the same surface oxidation state which confirms the robustness of the electrocatalyst. The reported results are far better than many of the transition metal oxides/chalcogenides electrocatalysts and hence it is expected that HNT could act as a potential alternative candidate to replace the benchmark platinum catalyst.
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Crystalline walled SBA-15 with large pore size were prepared using alkali and alkali earth metal ions (Na+, Li+, K+ and Ca2+). For this work, the ratios of alkali metal ions (Si/metal ion) ranged from 2.1 to 80, while the temperatures tested ranged from 500 to 700 °C. The SBA-15 prepared with Si/Na+ ratios ranging from 2.1 to 40 at 700 °C exhibited both cristobalite and quartz SiO2 structures in pore walls. When the Na+ amount increased (i.e., Si/Na increased from 80 to 40), the pore size was increased remarkably but the surface area and pore volume of the metal ion-based SBA-15 were decreased. When the SBA-15 prepared with Li+, K+ and Ca2+ ions (Si/metal ion = 40) was thermally treated at 700 °C, the crystalline SiO2 of quartz structure with large pore diameter (i.e., 802.5 Å) was observed for Ca+2 ion-based SBA-15, while no crystalline SiO2 structures were observed in pore walls for both the K+ and Li+ ions treated SBA-15. The crystalline SiO2 structures may be formed by the rearrangement of silica matrix when alkali or alkali earth metal ions are inserted into silica matrix at elevated temperature.
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Tunable multi-responsive mesoporous silica nanoparticles were prepared by post-condensation/surface modification of MCM-41 nanoparticles. Surface grafting of a poly(N,N-dimethylaminoethyl methacrylate)-based polymer containing disulfide bonds was achieved by a click reaction. Chemical modification, morphological characteristics, and textural properties of the nanoparticles were studied using multiple characterization techniques such as Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, small-angle X-ray scattering, and nitrogen adsorption/desorption behavior. The nanoparticles retained the meso-structural integrity of MCM41 and particle size < 100 nm after grafting with the polymer. The pH and redox-responsive behavior of the nanoparticles were also studied. The nanoparticles possess excellent drug-loading capacity owing to their large surface area and 'closed gate' mechanism of the grafted polymer chains. The release profile of doxorubicin at two different pH (7.4 and 5.5) and in the presence of dithiothreitol showed a dual response behavior. The nano drug carrier device exhibited efficient intracellular uptake in cancer cells with suitable cytotoxicity and pharmacokinetic behavior, and may therefore be considered a good candidate for cancer therapy.
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Portadores de Fármacos , Nanopartículas , Doxorrubicina/farmacología , Liberación de Fármacos , Porosidad , Dióxido de SilicioRESUMEN
Recently, the release of some metal ions to the environment has been observed to cause serious damages to human health and the environment. Herein, a chromium(VI)- and zinc(II)-selective adsorbent (CB18crown6/SBA-15) was successfully fabricated through the covalent attachment of 4'-carboxybenzo-18-crown-6 (CB18crown6) as a ligand on mesoporous silica support (SBA-15). The CB18crown6/SBA-15 adsorbent was characterized by Fourier-transform infrared (FTIR) spectrometry, X-ray diffraction (XRD), N2 adsorption-desorption, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). To evaluate its ability to selectively capture Cr(VI) and Zn(II), adsorption experiments were conducted. The influences of pH, initial concentration of metal ions, and coexisting metal ions on the adsorption process were examined. The CB18crown6/SBA-15 selectively adsorbed Cr(VI) at pH 2 and Zn(II) at pH 5, respectively, from the mixed aqueous solutions of chromium, zinc, lithium, cadmium, cobalt, strontium, and cesium ions. The data for the adsorption of Cr(VI) onto the CB18crown6/SBA-15 were well explained by the Langmuir adsorption isotherm. In addition, the recycling and reuse of CB18crown6/SBA-15 was successfully achieved, and 71 and 76% reuse efficiency of Cr(VI) and Zn(II), respectively, was obtained after five cycles. This study suggests that the use of the CB18crown6/SBA-15 can be a feasible approach for the selective remediation of Cr(VI) and Zn(II) contamination.
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In this study, free-radical polymerisation inside MCM-41 mesopores was examined to expose a construction route for a temperature-responsive switchable polymer-silica nanohybrid material with well-defined porosity. Herein, we introduced a vinyl monomer (N-isopropyl acrylamide), a cross-linker, and an AIBN initiator into the palladium nanoparticle incorporated MCM-41 pore channels using the wet-impregnation method followed by in situ radical polymerisation. The structural properties of the synthesised PNIPAM-PdNP-MCM-41 catalyst were analysed by various sophisticated analytical techniques. The temperature switchable nanohybrid catalyst was used to reduce carbonyl compounds to their corresponding alcohols. The catalyst showed high catalytic efficiency and robustness in an aqueous medium at 25 °C. Moreover, the system's polymer layer remarkably boosted catalytic selectivity and activity for carbonyl compound reduction as compared to other controlled catalysts. The suggested switchable system can be employed as a temperature-controllable heterogeneous catalyst and highlights a substitute technique to counter the methodical insufficiency in switchable supported molecular catalytic system production.
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In this study, we examined the highly selective sensing of Fe3+ ions in water using metal complex-functionalized mesoporous silica materials. Metal complex-functionalized mesoporous silica materials were synthesized on the mesoporous surface of SBA-15 via complexation process between Eu3+ and aminosilane groups. Mesoporous silica, SBA-15, and the Eu3+-complex functionalized SBA-15 were characterized using X-ray diffraction (XRD), transmittance electron microscopy (TEM), nitrogen sorption behavior, and Fourier transform infrared (FTIR) spectroscopy. The sensing behavior of the Eu3+-complex functionalized SBA-15 was studied using various metal ions (Fe3+, Cu2+, Cr3+, Co2+, Hg2+, Pb2+, and Zn2+) aqueous solutions. Photoluminescence intensity (λ = 612 nm) of the Eu3+-complex functionalized SBA-15 was dependent on the different interactions between metal ions and Eu3+-complexes. Photoluminescence intensity at λ = 612 nm of the Eu3+-complex functionalized SBA-15 decreased to near zero and proved the highly selective sensing effect of Fe3+. Therefore, the Eu3+-complex functionalized SBA-15 can be considered an excellent candidate for sensing iron ions in water.
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In this study, highly transparent siloxane-based hybrid UV-curable coating materials were prepared using (acryloxypropyl)methylsiloxane monomer (APMS), a thiol-ene monomer, with benzoin ethyl ether. For the thiol-ene monomer, either pentaerythritol tetrakis(3-mercaptopropionate) (PETTMP) or trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) was used. The siloxane-based hybrid coating materials were highly transparent and hard (pencil hardness of 6-7H). The materials were also amphiphobic, with a water static contact angle of 92-100° and an oil contact angle of 46-63°, when prepared with a high siloxane-monomer-to-PETTMP/TMPTMP ratio. In general, both hybrid coating materials exhibited improved oleophobicity, high hardness, and surface smoothness with increasing siloxane content, although the TMPTMP-based hybrid coating films exhibited slightly higher oleophobicity (lower hydrophobicity) and a smoother surface than the PETTMP-based hybrid coating films.
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Multi-structured platinum nanoclusters have been prepared through a one-step aqueous synthetic process by controlling pHs. The included structures are closely packed 3-dimensional (3D) dendrites, loosely packed 3D dendrites, short-order dendritic chains, long-order dendritic chains, flatten nanoclusters and monodisperse nanoparticles. The high resolution transmission electron microscopy images (HRTEM) display that the nanoclusters with a variety of structures are filled with grains of average size ~2.0 nm. The images of the nanoclusters demonstrated that Pt nanoparticles were not fused to each other, but their aggregations were separated by cetyltrimethylammonium bromide (CTAB). The as-prepared Pt nanomaterials were studied by UV-visible absorption spectroscopy to identify their surface plasmon resonance (SPR) activities. The structure dependent SPR signals have been observed from 200 nm-800 nm.
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Nanopartículas , Nanoestructuras , Microscopía Electrónica de Transmisión , Platino (Metal) , Resonancia por Plasmón de SuperficieRESUMEN
The control of surface wettability through a combination of surface roughness, chemical composition, and structural modification has attracted significant attention for antifogging and antibacterial applications. Herein, a two-step spin-coating method for amphiphilic organic-inorganic hybrid materials with incorporated transition metal ions is presented. The coating solution was prepared via photochemical thiol-ene click reaction between the mercapto functional group in trimethylolpropane tris(3-mercaptopropionate) and the vinyl functionalized silica precursor 3-(trimethoxysilyl)propyl methacrylate. In the first step of coating, a glass substrate was coated using a solution of metal nitrate hydrates and subsequently showed hydrophobic properties. As the second step, the spin-coated glass substrate was further coated with silica nanoparticles (SiO2 NPs) and polycaprolactone triol (PCT) suspension, where the contents of SiO2 NPs were fixed at 0.1 wt %, unless otherwise noted. The coated substrate exhibited hydrophilic properties. For comparison, the coating was also formulated with the SiO2 NPs/PCT suspension without SiO2 NPs and with 0.5 wt % SiO2 NPs as well as by adjusting different coating layer thicknesses. The surface morphology and chemical compositions of the obtained coating materials were analyzed by field emission scanning electron microscopy with energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The transparency and static contact angle of coated samples were measured by UV-visible spectrophotometry and drop shape analysis, respectively. It was concluded that our novel hybrid coating materials exhibited excellent antibacterial and antifogging properties with extremely high scratch resistance and transparency.
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Antibacterianos/farmacología , Materiales Biocompatibles Revestidos/farmacología , Escherichia coli/efectos de los fármacos , Compuestos Organometálicos/farmacología , Pseudomonas aeruginosa/efectos de los fármacos , Tensoactivos/farmacología , Antibacterianos/química , Materiales Biocompatibles Revestidos/química , Interacciones Hidrofóbicas e Hidrofílicas , Estructura Molecular , Compuestos Organometálicos/química , Tamaño de la Partícula , Propiedades de Superficie , Tensoactivos/químicaRESUMEN
The Prins cyclization of styrene (SE) with paraformaldehyde (PFCHO) was conducted with mesoporous ZnAlMCM-41 catalysts for the synthesis of 4-phenyl-1,3-dioxane (4-PDO) using a liquid phase heterogeneous catalytic method. For a comparison study, the Prins cyclization reaction was also conducted over different nanoporous catalysts, e.g. mesoporous solid acid catalysts, AlMCM-41(21) and ZnMCM-41(21), and microporous catalysts, USY, Hß, HZSM-5, and H-mordenite. The recyclable mesoporous ZnAlMCM-41 catalysts were reused in this reaction to evaluate their catalytic stabilities. Since ZnAlMCM-41(75) has higher catalytic activity than other solid acid catalysts, washed ZnAlMCM-41(75)/W-ZnAlMCM-41(75) was prepared using an efficient chemical treatment method and used with various reaction parameters to find an optimal parameter for the highly selective synthesis of 4-PDO. W-ZnAlMCM-41(75) was also used in the Prins cyclization of olefins with PFCHO and formalin (FN, 37% aqueous solution of formaldehyde (FCHO)) under different reaction conditions to obtain 1,3-dioxanes, which are widely used as solvents or intermediates in organic synthesis. Based on the nature of catalysts used under different reaction conditions, a reasonable plausible reaction mechanism for the Prins cyclization of SE with PFCHO is proposed. Notably, it can be seen from the catalytic results of all catalysts that the W-ZnAlMCM-41(75) catalyst has higher 4-PDO selectivity with exceptional catalytic activity than other microporous and mesoporous catalysts.
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Highly monodispersed silica nanoparticles (SiNPs) were synthesised using a fluorinated surfactant, HOCH2CH(CF3)CO2H, and its efficiency was compared with efficiencies of five other surfactants. The size of the SiNPs (â¼50-200 nm) was controlled by controlling the surfactant amount. The short alkyl-chain fluoro surfactant was found to be more efficient at producing monodispersed SiNPs than its long alkyl-chain fluoro or non-fluorinated surfactant counterparts.