Reversibly reducible cis-dichloroplatinum(II) and cis-dichloropalladium(II) complexes of bis(1-methylimidazol-2-yl)glyoxal

Complexes cis-MCl2(big), big=bis(1-methylimidazol-2-yl)glyoxal, M=Pt, Pd, were prepared and characterized through electrochemistry, spectroscopy, and for M=Pt, by X-ray structure analysis. The seven-membered chelate ring formed through N,N' coordination of the ligand big shows a boat conformation in agreement with density functional theory (DFT) calculation results. No significant intermolecular interactions were observed for the platinum compound. Both the PdII and PtII complexes undergo reversible one-electron reduction in CH2Cl2/ 0.1 M Bu4NPF6; the reduced palladium compound disintegrates above -30 degrees C. Electron paramagnetic resonance (EPR), UV-vis, and IR spectroelectrochemistry studies were employed to study the monoanions. The anion radical complex [cis-PtCl2(big)]*- exhibits a well-resolved EPR spectrum with small but well-detectable g anisotropy and an isotropic 195Pt hyperfine coupling of 12.2 G. DFT calculations confirm the spin concentration in the alpha-semidione part of the radical complex with small delocalization to the bis(imidazolyl)metal section. The results show that EPR and electroactive moieties can be linked to the cis-dichloroplatinum(II) group via imidazole coordination.     

Comparison of separation performance of polysaccaride-based chiral stationary phases in enantioseparation of 1-(4-chlorobenzhydryl)piperazine benzamide derivatives by HPLC

Analytical high-performance liquid chromatographic enantioseparation of 1-(4-chlorobenzhydryl) piperazine benzamide derivatives was accomplished on different chiral stationary phases. The enantiomers of the compounds were resolved by normal-phase chromatography on silica-based amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H), cellulose tris(3,5-dimethylphenylcarbamate) (Chiralcel OD-H) and cellulose tris(4-methylbenzoate) (Chiralcel OJ) columns with mobile phases consisting of mixtures of n-hexane and ethanol in different proportions (90: 10, 80: 20). The mobile phase and the chiral stationary phase were varied to achieve the best resolution. The effect of the concentration of ethanol in the mobile phase was studied. The resolution obtained on the three columns was significant.     

A robust alternative to the ratio estimator under non-normality

In sampling theory, the traditional ratio estimator is the most common estimator of the population mean when the correlation between study and auxiliary variables is positively high. We introduce a new ratio-type estimator based on the order statistics of a simple random sample. We show that this new estimator is considerably more efficient than the traditional ratio estimator under non-normality, and remarkably robust to data anomalies such as presence of outliers in data sets.     

Solvent and central metal effects on the photophysical and photochemical properties of 4-benzyloxybenzoxy substituted phthalocyanines

The synthesis and characterization of new peripherally tetra-4-benzyloxybenzoxy substituted metal-free, zinc and lead phthalocyanines are described for the first time in this study. The influence of various organic solvents and the nature of the central metal ion on the spectroscopic, photophysical and photochemical properties has been investigated. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in different solvents. Photophysical and photochemical properties of phthalocyanine compounds are very useful for photodynamic therapy applications. Especially high singlet oxygen quantum yields are very important for Type II mechanism. The studied phthalocyanine compounds showed good singlet oxygen generation and these compounds show potential as Type II photosensitizers. The fluorescences of the studied compounds are effectively quenched by 1,4-benzoquinone in different solvents.     

A closed form type reduction method for piecewise linear interval type-2 fuzzy sets

In this study, a new centroid type reduction method is proposed for piecewise linear interval type-2 fuzzy sets based on geometrical approach. The main idea behind the proposed method relies on the assumption that the part of footprint of uncertainty (FOU) of an interval type-2 fuzzy set (IT2FS) has a constant width where the centroid is searched. This constant width assumption provides a way to calculate the centroid of an IT2FS in closed form by using derivative based optimization without any need of iterations. When the related part of FOU is originally constant width, the proposed method finds the accurate centroid of an IT2FS; otherwise, an enhancement can be performed in the algorithm in order to minimize the error between the accurate and the calculated centroids. Moreover, only analytical formulas are used in the proposed method utilizing geometry. This eliminates the need of using discretization of an IT2FS for the type reduction process which in return naturally improves the accuracy and the computation time. The proposed method is compared with Enhanced Karnik–Mendel Iterative Procedure (EKMIP) in terms of the accuracy and the computation time on seven test fuzzy sets. The results show that the proposed method provides more accurate results with shorter computation time than EKMIP.     

Eco‐friendly Sensors Developed by Herbal Based Silver Nanoparticles for Electrochemical Detection of Mercury (II) Ion

In our study, the single‐use & eco‐friendly electrochemical sensor platform based on herbal silver nanoparticles (AgNPs) was developed for detection of mercury (II) ion (Hg²⁺). For this purpose, the surface of pencil graphite electrode (PGE) was modified with AgNPs and folic acid (FA), respectively. The concentrations of AgNPs and FA were firstly optimized by differential pulse voltammetry (DPV) to obtain an effective surface modification of PGE. Each step at the surface modification process was characterized by using cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS). The limit of detection (LOD) for Hg²⁺ was estimated and found to be 8.43 μM by CV technique. The sensor presented an excellent selectivity for Hg²⁺ against to other heavy metal ions such as Ca²⁺, Cd²⁺, Cr³⁺, Cu²⁺, Mg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, Co²⁺ and Mn²⁺. Moreover, a rapid, selective and sensitive detection of Hg²⁺ was successfully performed in the samples of tap water within 1 min.     

Supramolecular Coordination of Pb2+ Defects in Hybrid Lead Halide Perovskite Films Using Truxene Derivatives as Lewis Base Interlayers

Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb²⁺ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination.     

Degradation of substituted phenols with different oxygen sources catalyzed by Co(II) and Cu(II) phthalocyanine complexes

Research on substituted phenol degradations has received substantial attention. In this work, effective Co(II) and Cu(II) phthalocyanine complexes as catalysts were studied to degrade toxic phenols to harmless products. The effect of various process parameters, such as initial concentration of phenol, catalyst, oxygen sources, and temperature on the degradation reaction was investigated to achieve maximum degradation efficiency. The catalytic activities of Co(II) and Cu(II) phthalocyanines were evaluated for oxidation of phenolic compounds such as p-nitrophenol, o-chlorophenol, 2,3-dichlorophenol, and m-methoxyphenol. Co(II) phthalocyanine displayed good catalytic performance in degradation of 2,3-dichlorophenol to 2,3-dichlorobenzaldehyde and 2,3-dichloro-1,4-benzoquinone with the highest TON and TOF values within 3?h at 50?°C. The fate of catalyst during the degradation process was followed by UV–Vis spectroscopy.     

A new high‐performance blue to transmissive electrochromic material and use of silver nanowire network electrodes as substrates

Synthesis of a novel, high‐performance blue to transmissive switching electrochromic material is described. The polymer (P1) was prepared by both electrochemical ( P1E ) and chemical ( P1C ) means from the corresponding monomer. The electrochemically synthesized polymer ( P1E ) revealed 64% optical contrast change (on ITO) in the visible region and very fast switching times of 0.32 s (coloration) and 0.90 s (bleaching). On the other hand, the chemically synthesized, solution processable polymer ( P1C ) also showed a high optical contrast value (49%, on ITO) with very fast switching times of 0.86 s for coloration and 0.57 s for bleaching. These high optical contrast values coupled with fast switching times place these materials along with high‐performance blue to transmissive electrochromic polymers. Significantly, these improved characteristics were achieved by side chain engineering of a known, inferior blue to transmissive polymer, PBEBT. Towards fabrication of flexible electrochromic devices, the performance of P1C was also tested on silver nanowire network electrodes. Even though the full potential of the material could not be demonstrated, a good optical contrast of 24% was achieved using these electrodes. Under the same potential range allowed by silver nanowire network electrodes, P1C on ITO showed an optical contrast of 30%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1680–1686