Hydrothermal Deoxygenation of Graphene Oxide: Chemical and Structural Evolution

A green and facile approach for the partial deoxygenation of graphene oxide (GO) at moderate temperature (100 °C) and under atmospheric pressure, catalyzed by acidic conditions in water is reported. The chemical and structural changes in GO as a function of hydrothermal time were probed to understand the deoxygenation events. The brown GO dispersion in water was found to gradually turn black over the hydrothermal‐treatment time on account of the increasing graphitic content. FTIR, thermogravimetric (TG), Raman, and XRD analyses revealed that the labile oxygen functionalities are progressively eliminated, thereby partially restoring the π‐conjugated network. This was further corroborated by X‐ray photoelectron spectroscopy (XPS) studies based on quantitative analysis of each carbon component associated with the different chemical functionalities. Carbonyl, carboxyl, ether, and phenolic groups were found to be thermally stable, which hinders complete deoxygenation of GO and makes their dispersion in water stable, as monitored by the ζ potential. It is worth noting that deoxygenation events are expedited under acid‐catalyzed hydrothermal treatment relative to thermal deoxygenation in air.     

Highly selective enrichment of phosphopeptides using poly(dibenzo‐18‐crown‐6) as a solid‐phase extraction material

A poly(dibenzo‐18‐crown‐6) was used as a new solid‐phase extraction material for the selective enrichment of phosphopeptides. Isolation of phosphopeptides was achieved based on specific ionic interactions between poly(dibenzo‐18‐crown‐6) and the phosphate group of phosphopeptides. Thus, a method was developed and optimized, including loading, washing and elution steps, for the selective enrichment of phosphopeptides. To assess this potential, tryptic digest of three proteins (α‐ casein, β‐casein and ovalbumin) was applied on poly(dibenzo‐18‐crown‐6). The nonspecific products were removed by centrifugation and washing. The spectrometric analysis was performed using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Highly selective enrichment of both mono‐ and multiphosphorylated peptides was achieved using poly(dibenzo‐18‐crown‐6) as solid‐phase extraction material with minimum interference from nonspecific compounds. Furthermore, evaluation of the efficiency of the poly(dibenzo‐18‐crown‐6) was performed by applying the digest of egg white. Finally, quantum mechanical calculations were performed to calculate the binding energies to predict the affinity between poly(dibenzo‐18‐crown‐6) and various ligands. The newly identified solid‐phase extraction material was found to be a highly efficient tool for phosphopeptide recovery from tryptic digest of proteins.     

Ferroelectric studies for soft Gd-modified PZT ceramics

The polycrystalline samples of gadolinium-modified lead–zirconate–titanate (Pb_1?xGd_x (Zr_0.52Ti_0.48)_1?x/4O₃) (x?=?0, 0.07, 0.10 and 0.12) (PGZT x/52/48) ceramics near morphotropic-phase boundary were prepared using conventional solid-state reaction route. XRD patterns show the formation of single-phase compounds in rhombohedral crystal system. SEM textures of the samples reveal uniform grain distribution. Frequency and temperature dependence of dielectric constant of the materials indicates non-relaxor behavior and indication of the diffuse phase transition at higher values of Gd concentration. The temperature dependence of P–E loops confirms ferroelectricity in the materials. The piezoelectric studies of the samples show enhancement in piezoelectric coefficients on substitution of Gd at the Pb site.     

Studies of structure,dielectric and conduction mechanism of Bi3+/Yb3+ modified BaTiO3

The present communication aims at the study of the structural, dielectric, electrical and conduction properties of Bi³⁺/Yb³⁺ substituted BaTiO₃ with a chemical composition of Ba_0.5Bi_0.5Yb_0.5Ti_0.5O₃. The modified BaTiO₃, could be synthesized by a solid state reaction technique. The X-ray diffraction data and pattern revealed the formation of the above compound with tetragonal crystal system. The material's molecular structure (Ba–Ti–O bond, O–Ti–O stretching-mode, metal-oxygen bond, optical band gap, and so on) was determined using room temperature Fourier transform infrared (FTIR) and UV–visible spectroscopic spectra. Detailed investigations of the material's electrical (dielectric/leakage current and impedance) behavior over a wide temperature (25⁰C–500⁰C) and frequency (1 kHz–1000 kHz) range revealed the presence of capacitive, resistive, and conductive mechanisms. On the investigation of the polarization-electric field (P-E) hysteresis loop on multiple substitution, the change of ferroelectric polarization (spontaneous and residual) and storage density of BaTiO₃ was observed. Defect chemistry of the modified barium compound has been discussed in the details.     

Controlled processing of polymer nanoribbons: Enabling microhelix transformations

Flow‐coated, two‐dimensional polymer ribbon structures undergo a shape‐transformation into a three‐dimensional helix upon their release into a solution. Driven by surface forces and due to geometric asymmetry, the helix radius and spring constant depend upon the ribbon cross‐section dimensions, surface energy, and material elastic modulus. Such spring‐like microhelices offer multiple functionalities combined with mechanical stretching and shape recovery. Fabricating such microhelices requires a sequence of processing steps, beginning with flow‐coating of ribbons on a substrate, followed by etching of a “scum layer” to allow for an independent release into a solution, upon which shape‐transformation occurs. During the deposition‐etch‐release sequence, various control parameters influence the nanoribbon size and geometry, hence the helix properties. The experimental study presented here focuses on the influence of meniscus height, substrate velocity, substrate surface energy, and etch time on nanoribbon size (height and width), scum layer thickness, and helix radius. The results show that meniscus height and contact angle dictate flux toward the meniscus edge and volume available for spatial assembly, allowing control over the aspect ratio of ribbons. We vary the aspect ratio by two orders of magnitude, while maintaining geometric asymmetry needed for helix shape‐transformation. We provide robust scaling for the nanoribbon size and geometry and report the advantages and disadvantages of different parameters, in the control of polymer nanoribbon and helix fabrication. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1270–1278     

The functionality of the hybrid systems driven by molecular dimension of the guest copper Schiff‐base complexes entrapped in Zeolite‐Y

On encapsulation inside the supercage of zeolite‐Y planar Cu (II)–Schiff base complexes show the modified structural, optical and functional properties. The electronic effect of the different substituent groups present in the catalyst plays the decisive role towards their reactivity in the homogeneous phase but after the encapsulation in zeolite Y, reactivity is mainly governed by the molecular dimensions of the guest complexes rather than the electronic factor of the substituent groups attached on them. These systems are well characterized with the help of different characterization tools like XRD analysis, SEM ‐ EDX, AAS, FTIR, XPS, DSC, TGA, BET and UV–Visible spectroscopy and the comparative optical and catalytic studies have provided a rational explanation of enhanced reactivity of zeolite encapsulated metal complexes for various oxidation reactions compared to their corresponding solution states.