Differential electrochemical behaviour of phytofabricated and chemically synthesized silver nanoparticles towards hydrogen peroxide sensing**

Silver nanoparticles (AgNPs) are one of the most widely used nanomaterials for biomedical applications. However, the impact of its synthesis by chemical and plant-mediated routes on its differential electrochemical behaviour has not been examined till date. Here, we report for the first time the differential study of the electrochemical behaviour of the AgNPs synthesized by different routes. First, the AgNPs were obtained by different routes (chemical and phytofabrication) and extensively characterized to compare their physical properties. Thereafter, a comparison of electron transfer kinetics between chemically synthesized (Ag−C) and phyto-fabricated (Ag-Phy) nanoparticles (NPs) has been studied by electrochemical techniques such as potentiodynamic cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). To further investigate the electrocatalytic properties of both types of AgNPs, we have used the peroxide moieties (H₂O₂), and the Ag−C NPs-based sensor probe has been reported to have four times better sensitivity than the Ag−Phy NPs-based sensor. The AgNPs modified sensor probes have also been tested in real-world environments to explore the consistency of their performance in complex matrices by using clinical urine samples, where we found comparable sensitivity to the standard conditions.     

Weakly relaxed α-pseudomonotonicity and equilibrium problem in Banach spaces

In this paper, we introduce the weakly relaxed ??-pseudomonotone mapping which generalizes the class of pseudomonotone mappings. Some examples are given which show that the weakly relaxed ??-pseudomonotonicity is a proper generalization of pseudomonotonicity for both scalar and vector valued bi-functions. Using the KKM technique, we establish the existence of solutions of equilibrium problems and vector equilibrium problems with weakly relaxed ??-pseudomonotonicity in the reflexive Banach spaces. The present work extends some corresponding results of the variational-like inequalities (Fang and Huang in J. Optim. Theory Appl. 118:327?C338, 2003; Lee and Lee in J. Korea Soc. Math. Educ. Ser. B Pure Appl. Math. 11: 231?C242, 2004) to equilibrium problems.     

A Taco Complex Derived from a Bis-Crown Ether Capable of Executing Molecular Logic Operation through Reversible Complexation

As learned from natural systems, self-assembly and self-sorting help in interconnecting different molecular logic gates and thus achieve high-level logic functions. In this context, demonstration of important logic operations using changes in optical responses due to the formation of molecular assemblies is even more desirable for the construction of a molecular computer. Synthesis of an appropriate divalent as well as a luminescent crown ether based host 1 and paraquat derivatives, 2(PF(6))(2) and 3(PF(6))(2), as guests helped in demonstrating a reversible [3](taco complex) (1·{2(PF(6))(2)}(2) or 1·{3(PF(6))(2)}(2)) formation in nonpolar solvent. Detailed (1)H NMR studies revealed that two paraquat units were bound cooperatively by the two crown units in 1. Because of preorganization, the flexible host molecule 1 adopts a folded conformation, where each of two paraquat units remain sandwiched between the two aromatic units of each folded crown ether moiety in 1. Disassembly of the "taco" complex in the presence of KPF(6) and reassembly on subsequent addition of DB18C6 was initially demonstrated by (1)H NMR spectral studies, which were subsequently corroborated through luminescence spectral studies. Further, luminescence spectral responses as output signals with appropriate and two independent molecular inputs could be correlated to demonstrate basic logic operation like OR and YES gates, while the results of the three molecular inputs could be utilized to demonstrate important logic operation like an INHIBIT gate.     

Influence of Helium-Neon Laser Irradiation on Seed Germination In Vitro and Physico-Biochemical Characters in Seedlings of Brinjal (Solanum melongena L.) var. Mattu Gulla

In the present study, the seeds of brinjal (Solanum melongena L.) var. Mattu Gulla were irradiated with single exposure of He–Ne laser at different doses of 5–40 J cm^?2 and germinated aseptically. Thirty day old seedlings were harvested and the germination, growth, physiological and biochemical parameters were estimated and compared with un‐irradiated control seedlings. A significant enhancement in growth characters were noted with respect to length, fresh and dry weight of shoots and roots. In addition, chlorophyll (a and b), carotenoid content, anthocyanin and amylases (α and β) activities were found to be altered. Significant alterations in percentage of seed germination (P < 0.001) and time to 50% germination (P < 0.001) were observed in the irradiated seeds compared with the un‐irradiated controls. In conclusion, the results of the present study demonstrated that low dose (5–30 J cm^?2) of He–Ne laser irradiation enhanced the germination process and altered growth, by positively influencing physiological and biochemical parameters of the brinjal seedlings compared with un‐irradiated control under in vitro conditions.     

Effect of Fluorine Substitution on Absorption and Emission Properties of Figure-eight-shaped [5]Helicene Dimer: A Computational Study at RI-MP2/RI-ADC(2) Level

Chirality is a very important characteristic of optically active molecules and polyaromatics with helical structures, and plays a vital role in various applications in material science. In the present work, we show the effects of fluorine substitution at various positions in a figure-8-shaped [5]helicene dimer on the ground and excited state g-factors. Calculations for the ground and excited states are performed at the MP2 and ADC(2) levels of theory, respectively. The results reveal that fluorination has a large effect on the excited state structures. The values of the excited state dissymmetry factors for the molecules with fluorinations at both ends of the figure-8 systems are smaller than that of the parent system. On the other hand, fluorinations only in the stacked-phenyl region results in an increase in the value of . The perfluorinated system shows the smallest .