Competition Kinetics: An Experimental Approach

In this chapter, free radical kinetics with the help of competition kinetics and some experimental results calculated by competition kinetics to find out the rate constant of reactive species (●OH, eaq−, ●H) with target compound, which is used by radiation chemists is briefly discussed. The competition kinetics method is well validated by taking ciprofloxacin, norfloxacin and bezafibrate as example compounds. The bimolecular rate constants of hydroxyl radical, hydrate electron and hydrogen atom has been calculated for example solute species (ciprofloxacin, norfloxacin and bezafibrate)

The impact of immediate breast reconstruction on the time to delivery of adjuvant therapy: the iBRA-2 study

Background: Immediate breast reconstruction (IBR) is routinely offered to improve quality-of-life for women requiring mastectomy, but there are concerns that more complex surgery may delay adjuvant oncological treatments and compromise long-term outcomes. High-quality evidence is lacking. The iBRA-2 study aimed to investigate the impact of IBR on time to adjuvant therapy. Methods: Consecutive women undergoing mastectomy ± IBR for breast cancer July–December, 2016 were included. Patient demographics, operative, oncological and complication data were collected. Time from last definitive cancer surgery to first adjuvant treatment for patients undergoing mastectomy ± IBR were compared and risk factors associated with delays explored. Results: A total of 2540 patients were recruited from 76 centres; 1008 (39.7%) underwent IBR (implant-only [n = 675, 26.6%]; pedicled flaps [n = 105,4.1%] and free-flaps [n = 228, 8.9%]). Complications requiring re-admission or re-operation were significantly more common in patients undergoing IBR than those receiving mastectomy. Adjuvant chemotherapy or radiotherapy was required by 1235 (48.6%) patients. No clinically significant differences were seen in time to adjuvant therapy between patient groups but major complications irrespective of surgery received were significantly associated with treatment delays. Conclusions: IBR does not result in clinically significant delays to adjuvant therapy, but post-operative complications are associated with treatment delays. Strategies to minimise complications, including careful patient selection, are required to improve outcomes for patients

Solvent Catalysis in the Sensitizer-Mediator Redox Kinetics

The sensitizer-mediator redox reaction is a vital component of the dye-sensitized solar cells (DSSCs). The efficiency and stability of dye-sensitized solar cells are aided by the kinetics of this redox process. Several reaction parameters influence the kinetics of a reaction, and if those parameters are controlled, the rate of the process and its results can be controlled. One of the most important aspects of the sensitizer-mediator interaction is the reaction medium. Aqueous DSSCs are unquestionably a good replacement when it comes to taking a green approach to avoiding toxic, flammable, and volatile organic solvents and their mixtures, which are commonly used in DSSCs and are known to harm the environment while also reducing the lifetime and stability of the DSSCs. The catalytic role of a small volume fraction of organic solvent in the aqueous electron transfer kinetics of a few putative sensitizer-mediator reactions is discussed in this chapter. In binary solvent media including dilute tertiary butyl alcohol (TBA)-water and dilute 1,4-dioxane-water, the reduction of dicyanobis(2,2′-dipyridyl)iron(III) and dicyanobis(1,10-phenanthroline)iron(III) was investigated. The reactions were carried out in a 10% TBA or dioxane to water media with a volume-volume fraction of both solvents using iodide as a reducing agent. The effect of several parameters on the rate constant was also calculated and analyzed

Catalytic Behavior of Extended π-Conjugation in the Kinetics of Sensitizer-Mediator Interaction

This chapter discusses the catalytic effect of extended π-conjugation on the electron transfer process between ferricyphen-ferrocyanide and ferricypyr-ferrocyanide in an aqueous medium. Ferricyphen and ferricypyr may be feasible options for the sensitizer in dye-sensitized solar cells due to their high reduction potential, stability, capability as an outer-sphere oxidant, and photosensitivity. Meanwhile, ferrocyanide could be used as a mediator in DSSCs instead of iodide to avoid iodate production and achieve a similar reduction potential and stability. This chapter compared the ability of competent putative sensitizers to oxidize the likely mediator in water. In contrast to the 2,2′-dipyridyl chelate, the extended π-conjugation in 1,10-phenanthroline accelerated the redox process by increasing the electron affinity of ferricyphen as compared to ferricypyr. The reactions had the same kinetics but different rate constants, indicating that the ferricyphen-ferrocyanide reaction was several times faster than the ferricypyr-ferrocyanide reaction, revealing and confirming the catalytic influence of extended π-conjugation on the redox process

Synthesis, Characterization, and Solar Photo-Activation of Chitosan-Modified Nickel Magnetite Bio-Composite for Degradation of Recalcitrant Organic Pollutants in Water

Photocatalysis is a promising process for decomposing harmful organic pollutants in water. In this study, solar/photocatalytic degradation of two model azo dyes, i.e., methylene blue (MB) and methyl red (MR), in water usinga nanostructured chitosan-modified nickel magnetite (CS-NM) bio-composite was investigated. The CS-NM bio-composite was synthesized through a co-precipitation method and characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermogravimetry (TGA), and UV-Vis spectroscopy. FTIR analysis showed the uniform incorporation and conjugation of nickel magnetite (NM) into the chitosan (CS) polymer matrix. SEM showed that the average particle size was 0.5 μm. The TGA results revealed the good thermal stability of the prepared bio-composite at 300 °C. The point of zero charge was calculated as 7.5. The effect of water quality and process parameters, such as concentration of dyes, catalyst dose, solution pH, and temperatures, was investigated, for application purposes. The solar/CS-NM photocatalysis resulted in 99 and 96% degradation of individual MB and MR (C0 = 50 ppm), respectively, in 90 min. The degradation of MB and MR by solar/CS-NM photocatalysis followed pseudo-first-order kinetics, with observed rate constants (k) of 0.077 and 0.072 min−1, respectively. The CS-NM photocatalyst showed high recyclability, represented by only a 4–6% loss in the photocatalytic efficiency, after four cycles. The results showed that solar/CS-NM photocatalysis is an efficient technique for degrading recalcitrant organic pollutants, such as azo dyes, in water environments

Preparation of Electrochemical Supercapacitor Based on Polypyrrole/Gum Arabic Composites

The current research focused on the super capacitive behavior of organic conducting polymer, i.e., polypyrrole (PPy) and its composites with gum arabic (GA) prepared via inverse emulsion polymerization. The synthesized composites material was analyzed by different analytical techniques, such as UV-visible, FTIR, TGA, XRD, and SEM. The UV-Vis and FTIR spectroscopy clearly show the successful insertion of GA into PPy matrix. The TGA analysis shows high thermal stability for composites than pure PPy. The XRD and SEM analysis show the crystalline and amorphous structures and overall morphology of the composites is more compact and mesoporous as compared to the pure PPy. The electrochemical properties of modified solid state supercapacitors established on pure polypyrrole (PPy), polypyrrole/gum arabic (PPy/GA) based composites were investigated through cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge–discharge (GCD). The specific capacitance of the PPy modified gold electrode is impressive (~168 F/g). The specific capacitance of PPy/GA 1 electrode has been increased to 368 F/g with a high energy density and power density (~73 Wh/kg), and (~599 W/kg) respectively

Synthesis, Characterization and Evaluation of Supercapacitive Response of Dodecylbenzenesulphonic Acid (DBSA) Doped Polypyrrole/Zirconium Dioxide Composites

An in-situ chemical oxidative method was used to effectively synthesize a promising supercapacitor material based on PPy/ZrO2 composites. The synthesized materials were characterized by different analytical techniques, such as UV/visible (UV/Vis) spectroscopy, Fourier-transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The inclusion of ZrO2 into the PPy matrix was verified by vibrational spectra and structural analyses. The (TGA) results showed that incorporating ZrO2 into the polymeric matrix improved its thermal stability. In addition, the electrochemical properties of the synthesizedmaterials were investigated byusing cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD). The PPy/ZrO2 composite demonstrated excellent super capacitive performance, and high specific capacity of 337.83 F/g, with an exceedingly high energy density of 187.68 Wh/kg at a power density of 1000 W/kg. The composite materials maintain good stability after 1000 charge and discharge cycles, with 85% capacitance retention. The PPy/ZrO2 possesses a high capacitance, an attractive micro-morphology, and a simple synthesis method. The findings indicate that the PPy/ZrO2 composite could be a promising electrode material for high-performance supercapacitor applications