Voltammetric Study and Rapid Quantification of Resorcinol in Hair Dye and Biological Samples Using Ultrasensitive Maghemite/MWCNT Modified Carbon Paste Electrode

Increased concern over the risk resorcinol (RS) pose to ecology and humans, led to its position in European Union Category 1 list of endocrine disruptors. Legal measures restricted RS utilization and hence crucial to monitor its levels in the environment. Herein we report development of highly efficient and economically viable electrochemical sensor for quantitative determination of RS based on 77Maghemite/MultiWall Carbon Nanotube (M/MWCNT) modified carbon paste electrode. M/MWCNT was synthesized via strategic IR irradiation for the first time, a promising approach to overcome other complicated chemical routes. Powder X‐ray diffraction (PXRD), Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and Energy dispersive X‐ray (EDX) were used for characterization. Using Differential Pulse Voltammetry (DPV), we report the lowest detection limit at 0.02 μM. The potential application of the sensor was accomplished as a result of excellent recoveries made from real samples fortified with RS. Results indicated the proficiency of the sensor reliable for rapid, onsite monitoring of RS water contamination and in biological matrices.     

Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

Rheological characteristics of CeO2, Al2O3 and their hybrid mixture in ethylene glycol base fluid in the wide range of temperature and concentration

Journal of Thermal Analysis and Calorimetry - In the present work, the rheological behaviour of three different categories of nanofluid samples, 25 nm CeO2/EG, 13 nm Al2O3/EG and...     

Understanding guest and pressure‐induced porosity through structural transition in flexible interpenetrated MOF by Raman spectroscopy

Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)_0.5 · DMF(H₂O)_0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO₂ and its librational mode at 149 cm⁻¹ suggests cooperative adsorption of CO₂ in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd.     

Laser‐Induced Self‐Assembled Nanostructures on Electron‐Transparent Substrates

Currently, one of the challenges in high‐resolution transmission electron microscopy (TEM) studies of nanomaterials is to make contamination‐free materials in a simple and time‐efficient way. Here, a method is demonstrated that combines nanosecond‐pulsed laser dewetting of thin films with a film float‐off technique to realize nanostructures (NSs) on electron‐transparent substrates in a robust and rapid manner. NSs of metal (Ag) and bimetals (AgCo, AuCo) ranging from 20 to 150 nm are synthesized on thin carbon film deposited on mica substrates. The NS/carbon system is subsequently transferred onto TEM grids by a float‐off process resulting from debonding of the carbon from mica due to their contrasting hydrophobic nature. This process enables the fabrication of different NSs on flexible and electron‐transparent substrates.     

Pimprinols A–C,from the terrestrial actinomycete,Streptomyces sp.

A Streptomyces sp. Lv3-13, isolated from the rhizosphere soil of the plant Mespilus germanica, has yielded three new pimprinine derivatives, named pimprinols A–C (1–3) and the unknown (2-aminophenyl)(2-ethyloxazol-5-yl) methanone (4) along with the known compounds 2-ethyl oxazole pimprinine and 2-propyl oxazole pimprinine. The structures of the compounds were elucidated based on spectroscopic methods including UV, HR-ESIMS and 1D, 2D NMR data. Compounds 1–4 were screened for antimicrobial and cytotoxic activities.     

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2‐bis(4‐pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol‐dipyridylethylene (PGL:DPE) and phloroglucinol‐phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single‐component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.     

Amine‐Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition

Flexible and dynamic porous coordination polymers (PCPs) with well‐defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation of versatile guest molecules through noncovalent interactions. PCPs thus provide a potential platform for molecular recognition. Herein, we report a flexible 3D supramolecular framework {[Zn(ndc)(o‐phen)]?DMF}_n (o‐phen=1,10‐phenanthroline, ndc=2,6‐napthalenedicarboxylate) with confined nanospaces that can accommodate different electron‐donating aromatic amine guests with selective turn‐on emission signaling. This system serves as a molecular recognition platform through an emission‐readout process. Such unprecedented tunable emission with different amines is attributed to its emissive charge‐transfer (CT) complexation with o‐phen linkers. In certain cases this CT emission is further amplified by energy transfer from the chromophoric linker unit ndc, as evidenced by single‐crystal X‐ray structural characterization.     

Bis(2‐but­yl‐N,N′‐diisopropyl­amidinato)dichloro­hafnium(IV)

The title compound, [Hf(C₁₁H₂₃N₂)₂Cl₂], is a monomeric hafnium(IV) complex containing two bidentate amidinate ligands and two cis Cl atoms. The crystals are triclinic (space group ) and there is one independent six‐coordinate monomer with a highly distorted octa­hedral geometry in the asymmetric unit. The reported structure is the first hafnium–amidinate complex to be characterized successfully by single‐crystal X‐ray diffraction.