Octahedral oligomeric silsesquioxane (OAPS and OG) - Polyimide hybrid nanocomposite films: Thermo-mechanical,dielectric and morphology properties

Abstract

The nano-sized SQS based polyimides have been successfully synthesized with different oxide groups such as phosphineoxide, sulfone and siloxane as in the backbone of polymer. The SQS-Polyimide nanocomposites prepared through the condensation process using amine and epoxy functionalized SQS as precursor. The presence of SQS in the resulting polyimide nanocomposites was confirmed by FTIR and XRD analyses. The presence of SQS and greatly enhances the char yield to an extent of 16% when compared to that of neat polyimide. The incorporation of SQS into polyimide lowered the value of dielectric constant from 3.31 to 2.09 at 1?MHz and the value of thermal expansion coefficient from 56.6 to 42.7?ppm/K. The composites sample prepared using 20?wt% SQS possess the lowest value of dielectric constant and CTE value. The hydrophobic nature of SQS contributes to lower the water uptake of composites from a value of 2.76 (neat polyimide) to 2.42 for POS-PI containing 20?wt% SQS. Further, the SQS polyimide composite systems possess the enhanced values of thermal stability and glass transition temperatures according their percentage weight. Data obtained from different studies, it is suggested that these hybrid composites can be used as an effective insulation materials for high performance microelectronics applications.     

Thermophysical, mechanical and dielectric studies on piperidinium p-hydroxybenzoate

Single crystals of recently identified nonlinear optical material, piperidinium p-hydroxybenzoate (PDPHB), were grown by solution cooling method. It crystallizes in a monoclinic system with a noncentrosymmetric space group Cc. Thermal stability and decomposition behavior of PDPHB are illustrated through thermogravimetric, differential thermal and differential calorimetric analysis. The thermal diffusivity, thermal conductivity, and specific heat capacity of the grown crystals, which are the three most important thermo-physical parameters in heat transfer calculations, are calculated by an improved photopyroelectric technique. The room temperature hardness test has been performed on crystallographic planes (200), (020), and (002) using Vickers microhardness tester and the results are analyzed through the classical Meyer’s law. The dielectric constant, dielectric loss, and ac conductivity are studied as a function of frequency (100 Hz to 1 MHz) and temperature (313–363 K). All these studies are performed for the first time and aimed to explore the useful and safe region of thermal, mechanical, and electrical properties to enhance effectiveness of PDPHB crystals for device fabrications.     

Bismaleimide/rice husk silica reinforced composites

Silica derived from the renewable resource rice husk is modified using stearic acid and N-[4-(chlorocarbonyl)phenyl]maleimide. These materials are used as fillers in the bismaleimide, 4,4′-bismaleimidodiphenylmethane (BMIM), and thermally cured. The thermogravimetric (TG) curves for polyBMIM/silica composites showed no pronounced changes compared to the TG curve for the pure polyBMIM. Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa, and Friedman methods are used to compute the activation energy (E _a) for degradation. Silica and surface-modified silica using stearic acid dispersed by ultrasonication increase the activation energy for degradation and show considerable influence on the thermal stability of cured BMIM. The long alkyl chain present in the stearic acid modified silica and the bulky spacer present in the chemically modified silica definitely alter the degradation process of cured BMIM. The SEM studies indicated uniform dispersion of the silica particles in the polyBMIM.     

A redox series of aluminum complexes: characterization of four oxidation states including a ligand biradical state stabilized via exchange coupling

Electrophilic activation and subsequent reduction of substrates is in general not possible because highly Lewis acidic metals lack access to multiple redox states. Herein, we demonstrate that transition metal-like redox processes and electronic structure and magnetic properties can be imparted to aluminum(III). Bis(iminopyridine) complexes containing neutral, monoanionic, and dianionic iminopyridine ligands (IP) have been characterized structurally and electronically; yellow (IP)AlCl(3) (1), deep green (IP(-))(2)AlCl (2) and (IP(-))(2)Al(CF(3)SO(3)) (3), and deep purple [(IP(2-))Al](-) (5) are presented. The mixed-valent, monoradical complex (IP(-))(IP(2-))Al is unstable toward C-C coupling, and [(IP(2-))Al](2-)(μ-IP-IP)(2-) (4) has been isolated. Variable-temperature magnetic susceptibility and EPR spectroscopy measurements indicate that the biradical character of the ligand-based triplet in 2 is stabilized by strong antiferromagnetic exchange coupling mediated by aluminum(III): J = -230 cm(-1) for ? = -2J(?(L(1))·?(L(2))). Coordination geometry-dependent (IP(-))-(IP(-)) communication through aluminum(III) is observed electrochemically. The cyclic voltammogram of trigonal bipyramidal 2 displays successive ligand-based oxidation events for the two IP(1-/0) processes, at -0.86 and -1.20 V vs SCE. The 0.34 V spacing between redox couples corresponds to a conproportionation constant of K(c) = 10(5.8) for the process (IP(-))(2)AlCl + (IP)(2)AlCl → 2(IP(-))(IP)AlCl consistent with Robin and Day Class II mixed-valent behavior. Tetrahedral 5 displays localized, Class I behavior as indicated by closely spaced redox couples. Furthermore, CV's of 2 and 5 indicate that changes in the coordination environment of the aluminum center shift the potentials for the IP(1-/0) and IP(2-/1-) redox couples by up to 0.9 V.     

Amperometric hydrogen peroxide and cholesterol biosensors designed by using hierarchical curtailed silver flowers functionalized graphene and enzymes deposits

Novel flower-like silver particles with triangular plates as building block along with functionalized graphene (straggled sheets) and enzymes horseradish peroxidase (HRP) or cholesterol oxidase (ChOx), were obtained on graphite electrode by galvanostatic electrodeposition method. The morphology of the electrodeposits has been characterized using scanning electron microscopy and energy-dispersive analysis of X-ray. The resulting biosensors named Nf/(HRP-f-graphene-Ag)/Gr and Nf/(ChOx-f-graphene-Ag)/Gr were evaluated for electrochemical activity using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. Optimization of the interdependent experimental parameters such as pH and temperature were achieved and maintained constant throughout the experiments. An activation energy of 2.5 kJ mol^?1 was obtained for Nf/(HRP-f-graphene-Ag)/Gr electrode while Nf/(ChOx-f-graphene-Ag)/Gr showed an activation energy of 2.06 and 3.12 kJ mol^?1. Furthermore, the former electrode demonstrated a good linear range of 25 μM to 19.35 mM with rapid response time of 3 s and detection limit of 5 μM for hydrogen peroxide. Similarly, the Nf/(ChOx-f-graphene-Ag)/Gr electrode revealed a linear range of 0.1–4.5 mM with rapid response time of 3 s and an excellent detection limit of 0.514 mM for cholesterol. Besides this, the Nf/(HRP-f-graphene-Ag)/Gr and Nf/(ChOx-f-graphene-Ag)/Gr electrodes displayed a Michaelis–Menten constant of 0.26 and 0.57 mM, respectively, suggesting high affinity and enzymatic activity. The enhanced performance of biosensors towards detection of substrate and rejection of interferents, provided an evidence for its high anti-interference ability. Additionally the biosensors exhibit long term storage stability and reproducibility with antifouling properties.     

Hydroxo‐Bridged Dimers of Oxo‐Centered Ruthenium(III) Triangle: Synthesis and Spectroscopic and Theoretical Investigations

The homometallic hexameric ruthenium cluster of the formula [Ru^III₆(μ₃‐O)₂(μ‐OH)₂((CH₃)₃CCO₂)₁₂(py)₂] ( 1 ) (py=pyridine) is solved by single‐crystal X‐ray diffraction. Magnetic susceptibility measurements performed on 1 suggest that the antiferromagnetic interaction between the Ru^III centers is dominant, and this is supported by theoretical studies. Theoretical calculations based on density functional methods yield eight different exchange interaction values for 1 : J₁=?737.6, J₂=+63.4, J₃=?187.6, J₄=+124.4, J₅=?376.4, J₆=?601.2, J₇=?657.0, and J₈=?800.6 cm^?1. Among all the computed J values, six are found to be antiferromagnetic. Four exchange values (J₁, J₆, J₇ and J₈) are computed to be extremely strong, with J₈, mediated through one μ‐hydroxo and a carboxylate bridge, being by far the largest exchange obtained for any transition‐metal cluster. The origin of these strong interactions is the orientation of the magnetic orbitals in the Ru^III centers, and the computed J values are rationalized by using molecular orbital and natural bond order analysis. Detailed NMR studies (¹H, ¹³C, HSQC, NOESY, and TOCSY) of 1 (in CDCl₃) confirm the existence of the solid‐state structure in solution. The observation of sharp NMR peaks and spin‐lattice time relaxation (T1 relaxation) experiments support the existence of strong intramolecular antiferromagnetic exchange interactions between the metal centers. A broad absorption peak around 600–1000 nm in the visible to near‐IR region is a characteristic signature of an intracluster charge‐transfer transition. Cyclic voltammetry experiments show that there are three reversible one‐electron redox couples at ?0.865, +0.186, and +1.159 V with respect to the Ag/AgCl reference electrode, which corresponds to two metal‐based one‐electron oxidations and one reduction process.     

Residual Metal Impurity Aids Facile In Situ Electrochemical Surface Derivatization of Single‐Walled Carbon Nanotubes

Residual metal impurities were exploited as reactants in the functionalization of the surface of single‐walled carbon nanotubes (SWCNT) with nickel hexacyanoferrate (NiHCF) by simple electrochemical cycling in ferricyanide solutions. This facile in situ electrochemical modification process provides intimate contact between NiHCF and SWCNTs that improves the stability of the redox property and reactivity of NiHCF. The characteristic redox behavior of NiHCF on SWCNT surfaces can be used as an electrochemical probe to access qualitative and quantitative information on unknown electroactive metal impurities in SWCNTs. Significantly, the NiHCF‐modified SWCNTs exhibit pseudocapacitive behavior, and the calculated specific capacitances are 710 and 36 F g^?1 for NiHCF‐SWCNTs and SWCNTs respectively. Furthermore, NiHCF‐SWCNTs were transformed into Ni(OH)₂/SWCNTs and used for enzymeless glucose oxidation.     

A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics

Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination.     

meso-(4-(N,N-dialkylamino)phenyl)-substituted subporphyrins: remarkably perturbed absorption spectra and enhanced fluorescence by intramolecular charge transfer interactions

A series of meso-(4-(N,N-dibenzylamino)phenyl)-substituted subporphyrins was synthesized by means of Buchwald-Hartwig amination protocol. Substitution of the amino group at the 4-position of the meso-phenyl substituent resulted in a remarkable red shift in the absorption spectra and drastic enhancement of fluorescence intensity probably as a consequence of intramolecular CT interaction. These characteristics have been utilized to construct a cation-sensing system by appending a 1-aza-15-crown-5 unit to subporphyrin that displays large spectral changes upon cation binding.     

Synthesis of copper dendrite nanostructures by a sonoelectrochemical method

Copper dendrites have been prepared by a sonoelectrochemical process from an aqueous solution of Cu(2+) in the presence of polyvinyl alcohol. A SEM image of the morpholohy of the copper formed on the electrode after one electric pulse is presented. A subsequent sonic pulse removes the copper from the electrode surface, cleaning it for the next step. The formation of the dendrites is accounted for by the "drying-mediated self-assembly of nanoparticles" theory.