Tetrahydrofuran Hydroperoxide Research Articles

Multigram Synthesis of a Combustion-Relevant δ-Ketohydroperoxide through Sulfonylhydrazine Substitution.

A synthesis of a δ-ketohydroperoxide is described, addressing potential functional-group compatibilities in these elusive species relevant to combustion and atmospheric chemistries. The hydroperoxide is installed via sulfonylhydrazine substitution, which was found to be more effective than displacement of secondary halides. As part of this protocol, it was observed that 1,2-dimethoxyethane is an advantageous medium for the reaction, avoiding the formation of a tetrahydrofuran hydroperoxide side product. This discovery facilitated the multigram synthesis (6 steps, 41 % yield overall) and discrete characterization of the target δ-ketohydroperoxide.

Synthesis and Applications of Processable Prussian Blue Nanoparticles

The present report describes a comparative study on chemical synthesis of processable Prussian blue Nanoparticles (PBNPs) suitable for developing PB-based devices. Controlled nucleation of PBNP from single precursors, Potassium hexacyanoferrate, has been recorded as a function of reducing and stabilizing ability of some active organic reducing agents. The use of organic reagent control the nucleation process yielding PBNPs displaying both homogeneous and heterogeneous catalysis. Four different systems of active organic reducing agents i.e.: (1) 3-aminopropyltrimethoxysilane (3-APTMS) and cyclohexanone, (2) tetrahydrofuran hydroperoxide, (3) tetrahydrofuran and hydrogen peroxide and (4) tetrahydrofuran hydroperoxide and 2-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane resulted the formation of PBNP1, PBNP2, PBNP3 and PBNP4 displaying sensitivity of analysis to the order of 480, 330 350 and 400 mA mM-1 cm-2 respectively.The as reported process also enable the controlled synthesis of noble metal nanoparticles introducing new rout for yielding Prussian blue-noble metal nanoparticle nanocomposite that manipulate the catalytic/elecrocatalytic activity for targeted system. As made PBNPs undergo the formation of homogeneous nanodispersion with gold nanoparticles and ruthenium bipyridyl with gradual enhancement in the catalytic activity. The typical application in probing glucose oxidase catalyzed reaction based on both homogeneous and heterogeneous catalysis has been recorded. In addition the synthetic approach could also be explored to incorporate Prussian blue and palladium nanoparticles in mesoporous matrix for developing variety of PB-based devices.

Synthesis and Applications of Processable Prussian Blue Nanoparticles

The present report describes a comparative study on chemical synthesis of processable Prussian blue Nanoparticles (PBNPs) suitable for developing PB-based devices. Controlled nucleation of PBNP from single precursors, Potassium hexacyanoferrate, has been recorded as a function of reducing and stabilizing ability of some active organic reducing agents. The use of organic reagent control the nucleation process yielding PBNPs displaying both homogeneous and heterogeneous catalysis. Four different systems of active organic reducing agents i.e.: (1) 3-aminopropyltrimethoxysilane (3-APTMS) and cyclohexanone, (2) tetrahydrofuran hydroperoxide, (3) tetrahydrofuran and hydrogen peroxide and (4) tetrahydrofuran hydroperoxide and 2-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane resulted the formation of PBNP1, PBNP2, PBNP3 and PBNP4 displaying sensitivity of analysis to the order of 480, 330 350 and 400 mA mM-1 cm-2 respectively.The as reported process also enable the controlled synthesis of noble metal nanoparticles introducing new rout for yielding Prussian blue-noble metal nanoparticle nanocomposite that manipulate the catalytic/elecrocatalytic activity for targeted system. As made PBNPs undergo the formation of homogeneous nanodispersion with gold nanoparticles and ruthenium bipyridyl with gradual enhancement in the catalytic activity. The typical application in probing glucose oxidase catalyzed reaction based on both homogeneous and heterogeneous catalysis has been recorded. In addition the synthetic approach could also be explored to incorporate Prussian blue and palladium nanoparticles in mesoporous matrix for developing variety of PB-based devices.

Palladium-Prussian blue nanoparticles; as homogeneous and heterogeneous electrocatalysts

We report herein a synthetic strategy based on the use of tetrahydrofuran hydroperoxide (THF-HPO) that allows controlled conversion of palladium ion and potassium ferricyanide into palladium nanoparticles (PdNP) and water soluble Prussian blue nanoparticles (PBNP) respectively. The results revealed that THF-HPO provide a medium to enable the transformation of 3-aminopropyltrimethoxysilane (3-APTMS) capped palladium ions into PdNP of desired nanogeometry viz. PdNP1 and PdNP2. The processability of these two types of nanomaterials enabled the formation of PB-PdNP1 and PB-PdNP2 having potentiality for use either as homogeneous suspension or in heterogeneous matrix. The results based on peroxidase mimetic activity, cyclic voltammetry and amperometry revealed the gradual improvement in analytical performances of as synthesized nanomaterials as a function of palladium size and has been characterized by TEM, HRSEM and EDX analysis.

Functional alkoxysilane mediated controlled synthesis of Prussian blue nanoparticles, enabling silica alginate bead development; nanomaterial for selective electrochemical sensing

We report herein the controlled synthetic strategy for Prussian blue nanoparticles (PBNPs) formation justifying the role of functional alkoxysilanes, [2-(3,4-Epoxycyclohexyl)ethyl]trimethoxysilane (EETMSi) in the presence of tetrahydrofuran hydroperoxide (THF-HPO) with following major findings: (i) significant change in nanogeometry from 40 to 8 nm by addition of EETMSi and (ii) allowed fabrication of PBNPs encapsulated silica-alginate beads. As made nanoparticles were characterized by UV–Vis spectroscopy, TEM, FT-IR, and SEM. Size dependent electrochemical behavior of three different PBNPs i.e. PBNPs-1 (26 nm), PBNPs-2 (17 nm) and PBNPs-3 (8 nm) was recorded based on cyclic voltammetry. Apart from unprecedented size-dependent properties, as made PBNPs-3 display excellent peroxidase mimetic activity with Km value to the order of ∼0.9 mM. In addition, EETMSi also allows to cast Prussian blue film and simultaneously enable the formation of silica-alginate beads with controlled pores size perfectly suitable for encapsulating these nanoparticles which allocate selective electrochemical oxidation of Pyrogallol (Py) at 0.3 V vs. Ag/AgCl.

Polyethylenimine-mediated synthetic insertion of gold nanoparticles into mesoporous silica nanoparticles for drug loading and biocatalysis.

Mesoporous silica nanoparticles (MSNPs) have been used as an efficient and safe carrier for drug delivery and biocatalysis. The surface modification of MSNPs using suitable reagents may provide a robust framework in which two or more components can be incorporated to give multifunctional capabilities (e.g., synthesis of noble metal nanoparticles within mesoporous architecture along with loading of a bioactive molecule). In this study, the authors reported on a new synthetic route for the synthesis of gold nanoparticles (AuNPs) within (1) unmodified MSNPs and (2) 3-trihydroxysilylpropyl methylphosphonate-modified MSNPs. A cationic polymer, polyethylenimine (PEI), and formaldehyde were used to mediate synthetic incorporation of AuNPs within MSNPs. The AuNPs incorporated within the mesoporous matrix were characterized by transmission electron microscopy, energy dispersive x-ray analysis, and high-resolution scanning electron microscopy. PEI in the presence of formaldehyde enabled synthetic incorporation of AuNPs in both unmodified and modified MSNPs. The use of unmodified MSNPs was associated with an increase in the polycrystalline structure of the AuNPs within the MSNPs. The AuNPs within modified MSNPs showed better catalytic activity than those within unmodified MSNPs. MSNPs with an average size of 200 nm and with a pore size of 4-6 nm were used for synthetic insertion of AuNPs. It was found that the PEI coating enabled AuNPs synthesis within the mesopores in the presence of formaldehyde or tetrahydrofuran hydroperoxide at a temperature between 10 and 25 °C or at 60 °C in the absence of organic reducing agents. The as-made AuNP-inserted MSNPs exhibited enhanced catalytic activity. For example, these materials enabled rapid catalytic oxidation of the o-dianisidine substrate to produce a colored solution in proportion to the amount of H2O2 generated as a function of glucose oxidase-catalyzed oxidation of glucose; a linear concentration range from 80 to 800 μM and a detection limit as low as 80 μM were observed. The mesoscale pores of the as developed AuNP-inserted MSNPs were also used to entrap the hydrophobic drug paclitaxel. The results of this study indicate the potential use of the AuNP-inserted MSNPs in biocatalysis and drug delivery.

Role of organic functionalities linked to alkoxysilane precursors in nanomaterials synthesis and their biomedical applications

ABSTRACTThe synthesis of biocompatible noble metal nanoparticles dispersible in a wide range of biological media with control of polycrystalinity and nanogeometry, pH sensitivity and salt tolerance has been a challenging requirements. The role of 3-aminopropyltrimethoxysilane (3-APTMS) and organic reducing reagents for real time synthesis of amphilic noble metal nanoparticles meeting these requirements are demonstrated justifying the following; (1) 3-APTMS capped noble metal ions are converted into respective metal nanoparticles in the presence of one of organic reducing agents i.e., cyclohexanone, tetrahydrofuran hydroperoxide (THF-HPO), formaldehyde, acetaldehyde, acetone, t-buty dimethyl keotone, 3-Glycidoxy-propyltrimethoxysilane (3-GPTMS); (2) 3-APTMS acts as micelle, promotes the interaction of metal ions with organic reducing agent, precisely controls the size of metal nanoparticles, pH sensititvity and salt tolerance and also provides a suitable medium for nanoparticles suspension, (3) the use of suitable organic reagent precisely controls the polarity of as made noble metal nanoparticles allowing specific biological interactions, and (4) 3-APTMS significantly increases the stability and controls the pH sensitivity and salt tolerance of metal nanoparticles. The as synthesized nanomaterials show potential viability in biomedical applications from many angles i.e. (a) as potential bioelectrocatalyst, (b) selective interaction with active proteins and cellular components, and (c) peroxidase mimetic.

Tetrahydrofuran hydroperoxide and 3-Aminopropyltrimethoxysilane mediated controlled synthesis of Pd, Pd-Au, Au-Pd nanoparticles: Role of Palladium nanoparticles on the redox electrochemistry of ferrocene monocarboxylic acid

Tetrahydrofuran hydroperoxide (THF-HPO) and 3-aminopropyltrimethoxysilane (3-APTMS) mediated controlled synthesis of palladium (Pd) and palladium-gold bimetallic (Pd-Au) nanoparticles are reported and characterized by TEM, AFM and UV-Vis spectroscopy. A comparative study on the formation of bimetallic nanoparticles via sequential and simultaneous reduction of metal salts is reported. The nanogeometry of as synthesized nanoparticles decreases with an increase in 3-APTMS concentration. The effect of variable nanogeometry of palladium nanoparticles (PdNPs) on the reversible redox electrochemistry of ferrocene monocarboxylic acid (Fc-COOH) is examined with major findings; (1) the homogeneous redox electrochemistry of Fc-COOH tend to become sluggish in the presence of 3-APTMS, (2) the presence of palladium significantly improve the reversible redox behavior of ferrocene derivative with considerable decrease in anodic and cathodic peaks separation, (3) there is an increase in electrocatalytic efficiency during electrochemical sensing of ascorbic acid as a function of nanogeometry and (4) the PdNPs also show admirable peroxidase mimetics activity with remarkable dependence of the same on 3-APTMS concentrations.

Tetrahydrofuran hydroperoxide mediated synthesis of Prussian blue nanoparticles: a study of their electrocatalytic activity and intrinsic peroxidase-like behavior

We report herein, tetrahydrofuran hydroperoxide (THF-HP) mediated conversion of potassium ferricyanide into Prussian blue nanoparticles (PBNPs). The new process allows controlled conversion of single precursor (i.e., potassium ferricyanide) into water dispersible PBNPs that demonstrates potential viability for use in both homogeneous and heterogeneous catalysis. The typical process involves the mixing of optimum concentrations of potassium ferricyanide and tetrahydrofuran hydroperoxide resulting into the formation of PBNPs under ambient conditions as characterized by UV-Vis spectroscopy, atomic force microscopy, transmission electron microscopy, XRD and cyclic voltammetry. The as synthesized PBNPs shows wide practical applications i.e. (1) homogeneous electrocatalysis of glutathione (GSH), (2) peroxidase-like catalytic activity for H2O2 detection, (3) colorimetric determination of GSH based on competitive reaction of o-dianisidine and GSH with H2O2, (4) electrocatalytic reduction of lipid hydroperoxides with better selectivity and sensitivity. The electrocatalytic and peroxidase mimetic abilities of these PBNPs promise a strong impact on practical biomedical devices.

Tunable functionality and nanogeometry in tetrahydrofuran hydroperoxide and 3-aminopropyl-trimethoxysilane mediated synthesis of gold nanoparticles; functional application in glutathione sensing.

Substantive research on controlled synthesis of noble metal nanoparticles displaying tunable functionality and nanogeometry has been a challenging requirement. We report herein a process involving the active role of tetrahydrofuran hydroperoxide (THF-HPO) and 3-aminopropyltrimethoxysilane (3-APTMS) that allows controlled synthesis of functional gold nanoparticles (AuNPs) with the following major findings: (1) an increase in 3-APTMS concentrations causes an increase in size whereas the same for THF-HPO shows the reverse effect; (2) different sizes of AuNPs at the same concentration of 3-APTMS can be made by controlling THF-HPO; (3) addition of 3-APTMS even after AuNPs synthesis allow control over nanogeometry; (4) formation of γ-butyrolactone (GBL) during nanoparticle synthesis which itself participates in AuNPs synthesis. Furthermore, the functionality and nanogeometry of the as synthesized AuNPs are utilized in glutathione sensing justifying the pivotal role of functionality as compared to nanogeometry.

Infrared and Raman spectra of tetrahydrofuran hydroperoxide

The hydroperoxide of tetrahydrofuran (THF) has been prepared from unstabilized THF by a simple procedure. It appears that there are no previous reports of vibrational spectra of THF hydroperoxide in the literature. Raman and infrared spectra of the compound are presented here. The prominent feature of the infrared spectrum is a very strong broad band centered at 3330 cm −1 attributed to the OO-H stretching mode. A strong Raman line at 884 cm −1 is assigned to the O-O stretching vibration. The corresponding infrared band is very weak. 300 MHz proton and 13C NMR spectra also have been recorded. The NMR spectra are consistent with the structure 2-hydroperoxytetrahydrofuran. Implications of the formation of the hydroperoxide during storing and handling of THF as a solvent for liquid chromatography and other applications are discussed.

Photocrosslinking of poly(2,3‐epithiopropyl methacrylate) by the oxidation of pendant episulfide groups

AbstractIn the photocrosslinking of poly(2,3‐epithiopropyl methacrylate) (PETMA) films the effect of the pendant episulfide group's oxidation on the crosslinking of PETMA was investigated. Thermal crosslinking of PETMA is promoted by peroxides such as benzoyl peroxide and hydrogen peroxide. IR spectrum of the crosslinked PETMA showed that the reaction proceeded through the oxidation of episulfide groups by the peroxides. The anthracene (An) sensitized photocrosslinking of PETMA films also proceeded via the oxidation of episulfide groups by singlet oxygen. It was found that residual tetrahydrofuran (THF) in the films remarkably increased the rate of the photocrosslinking and/or reduced the induction period. From the further investigation concerning casting solvents it was found that residual CS2, CCl4, and CHCl3 in films increased the rate of the photocrosslinking and/or reduced the induction period of the photocrosslinking. The disappearance rate of An in the films was also increased by the presence of residual CS2, CCl4, and CHCl3, differring from the result of THF. These results were explained by a difference in lifetime of singlet oxygen in the films. From the results were explained by a difference in lifetime of singlet oxygen in the films. From the results concerning the effects of hydroperoxides such as THF hydroperoxide and t‐butyl hydroperoxide on the photocrosslinking of PETMA films the acceleration effect of the residual THF was deduced to be due to the promotion of singlet oxygen‐oxidation of sulfide groups by protic compounds such as THF hydroperoxide and H2O in the THF.

Oxygen-initiated free-radical cyanoethylation of tetrahydrofuran

Oxygen has been used as an initiator of the free-radical cyanoethylation of tetrahydrofuran by acrylonitrile. It has been shown that the initiation takes place mainly through the decomposition of tetrahydrofuran hydroperoxide, which is formed in an autooxidation of tetrahydrofuran. The initiating activity of tetrahydrofuran hydroperoxide at various temperatures has been studied. Initation at 130 °C is the most effective. The initiating activities of tetrahydrofuran hydroperoxide and of tert-butyl hydroperoxide have been compared.

Redox Reaction of Tetrahydrofuran Hydroperoxide

Abstract 1) Reaction of tetrahydrofuran hydroperoxide with ferrous sulfate produced hexane-1, 6-diol-diformate (13.8%), which was formed by the dimerization of 3-formoxypropyl radical generated from 2-tetrahydrofuranoxy radical, and γ-butyrolactone (31.4%) and 4-hydroxybutanal (trace). 2) In the presence of metal halide, the dimerization of the 3-formoxypropyl radical did not occur and halogenation of the 3-formoxypropyl radical was observed. For example, when tetrahydrofuran hydroperoxide was reacted with cuprous chloride and cupric chloride, 3-formoxypropyl chloride was obtained in a yield of 42.3%. 3) It is worth nothing that under suitable experimental condition the chloro compound was obtained in a good yield. 4) Probable reaction process was discussed.

Tetrahydrofuran Hydroperoxide

Tetrahydrofuran Hydroperoxide