Electron Transfer Studies In Langmuir-Blodgett Films Of Metallosurfactants For Current Rectification, Corrosion Mitigation, And Water Oxidation

The work presented in this dissertation is focused on the design and synthesis of new redox-active amphiphilic architectures to optimize and understand the redox, electronic, and film formation properties for applications in current rectification, corrosion mitigation, and water oxidation. As such, new redox-active, and amphiphilic iron(III), cobalt(III), nickel(II), copper(II), and zinc(II) complexes were synthesized as precursors for Langmuir-Blodgett films used for the aforementioned applications. For the use in molecular rectification, amphiphilic copper(II) and nickel(II) complexes with [N2O2] ligand environment were synthesized. Homogeneous film formation ability was observed between ~20-25 mN/m pressure, with a film collapse observed at ~35 mN/m for both complexes. The presence of both ligand- and metal-based redox processes made the copper(II) complex a viable candidate for device fabrication. However, current vs. voltage (I/V) measurements obtained for Au|LB|Au assemblies resulted in a flat I/V curve, diagnostic of an insulating nature. Comparison of the frontier molecular orbital energy between the insulating copper(II) complex and a similar rectifying iron(III) complex provided insight as to the rectification mechanism. Considering the orbital arrangement, the singly occupied molecular orbital (SOMO) of the Cu(II) complex is energetically high to enable electron transfer, thus making it an insulator. For comparison purposes, the SOMO of Fe(III) is situated 1.0 eV above the Fermi level of the Au electrode allowing for easy electron transfer from electrode to molecule. Furthermore, the highest occupied molecular orbital (HOMO) of Cu(II) is situated 1.0 eV below the Au Fermi level and the insulating nature of the device confirms that the HOMO is not involved in electron transfer. Therefore, only the SOMO of the Fe(III) complex should be involved in electron transfer following an asymmetric current rectification mechanism. This observation confirms that the SOMOs of such molecules can act as electron acceptors to facilitate electron transfer and assist in current rectification. In this regard, to enhance the energy compatibility between the SOMO and the Fermi level of the Au electrode, a series of new asymmetric iron(III) complexes with [N2O2], [N3O], and [N3O2] coordination environments were synthesized. According to isothermal compression data, new complexes exhibited amphiphilic nature with collapse pressures between ~35-40 mN/m. Calculations performed based on the redox potentials of the complexes showed that the SOMO energies of the Fe(III) complexes with [N2O2] coordination environment were situated 0.4 eV above the electrode Fermi level, while the SOMO energies of other complexes were situated 0.8 eV above the Fermi level. The energetic compatibility of these SOMOs with electrode Fermi levels makes these complexes viable candidates for molecular current rectification. Therefore, Au|LB|Au assemblies can be used to identify the rectification behavior of theses complexes. Based on the knowledge that Cu(II) salophen-based complexes can insulate electron transfer and therefore preclude electron transfer, a series of amphiphilic Fe(III), Cu(II), and Zn(II) complexes were synthesized to be used as protective coatings in corrosion mitigation. Cyclic voltammetry experiments revealed that 11-layer LB films of the complexes can effectively passivate electron transfer to the surface in a better way than the ligand alone. Agar experiments revealed a low corrosion rate for LB film-coated iron plates, with no blue coloration in the complex-coated area after one week. The presence of K3Fe(CN)6 in the agar medium can form a Prussian blue complex with Fe2+ ions produced due to oxidation. Optical micrograph and SEM images showed considerably low rust formation on complex-coated iron plates compared to the bare iron plate. Weight loss measurement studies confirmed that 11 layers of the Fe(III) and Zn(II) complexes demonstrate the best corrosion mitigation ability, with respective corrosion inhibition efficiencies of 27 % and 30 %, while the ligand alone showed an inhibition efficiency of only 6 %. This observation suggests that metal coatings can function as passivating barriers to electron flow between the electrolyte and the iron plate. Similarly, the use of LB films in heterogeneous water oxidation was investigated using a phenolate-rich cobalt(III) complex. This complex demonstrated homogeneous film formation ability at ~30-35 mN/m, with a collapse pressure of 42 mN/m. Monolayer-deposited FTO electrodes supported water oxidation at an overpotential of 0.50 V. Gradual enhancement of catalytic activity was observed in up to 9 deposited layers. Upon application of a potential bias, the monolayer yielded an estimated turnover number of 54,000 ± 1,500 after one hour with a Faradaic efficiency of ~ 100 %. Although the molecular species were rearranging into an ultrathin catalytic layer, the presence of symmetric and asymmetric C-H vibrations in IRRAS spectra suggests that carbon-based residues act as modifiers, thus confirming that the ligand choice is relevant to obtain efficient and robust catalytic films for water oxidation. In summary, this dissertation research presented a new series of ligand designs varying from [N2O2], [N3O], and [N3O2] and their iron(III), cobalt(II), nickel(II), copper(II), and zinc(II) complexes, which exhibit both redox and amphiphilic character. Further, this project investigates their LB film formation ability and use of these films on solid substrates in molecular electronics, corrosion mitigation, and heterogeneous water oxidation

Dendrimer-based Nanoparticle for Dye Sensitized Solar Cells with Improved Efficiency

Dye sensitized solar cells were fabricated with DyLight680 (DL680) dye and its corresponding europium conjugated dendrimer, DL680-Eu-G5PAMAM, to study the effect of europium on the current and voltage characteristics of the DL680 dye sensitized solar cell. The dye samples were characterized by using Absorption Spectroscopy, Emission Spectroscopy, Fluorescence lifetime and Fourier Transform Infrared measurements. Transmission electron microscopy imaging was carried out on the DL680-Eu-G5PAMAM dye and DL680-Eu-G5PAMAM dye sensitized titanium dioxide nanoparticles to analyze the size of the dye molecules and examine the interaction of the dye with titanium dioxide nanoparticles. The DL680-Eu-G5PAMAM dye sensitized solar cells demonstrated an enhanced solar-to-electric energy conversion of 0.32% under full light illumination (100 mWcm−2, AM 1.5 Global) in comparison with that of DL680 dye sensitized cells which recorded an average solar-to-electric energy conversion of only 0.19%. The improvement of the efficiency could be due to the presence of the europium that enhances the propensity of dye to absorb sunlight

Duchenne muscular dystrophy from brain to muscle: The role of brain dystrophin isoforms in motor functions

Brain function and its effect on motor performance in Duchenne muscular dystrophy (DMD) is an emerging concept. The present study explored how cumulative dystrophin isoform loss, age, and a corticosteroid treatment affect DMD motor outcomes. A total of 133 genetically confirmed DMD patients from Sri Lanka were divided into two groups based on whether their shorter dystrophin isoforms (Dp140, Dp116, and Dp71) were affected: Group 1, containing patients with Dp140, Dp116, and Dp71 affected (n = 98), and Group 2, containing unaffected patients (n = 35). A subset of 52 patients (Group 1, n = 38; Group 2, n = 14) was followed for up to three follow-ups performed in an average of 28-month intervals. The effect of the cumulative loss of shorter dystrophin isoforms on the natural history of DMD was analyzed. A total of 74/133 (56%) patients encountered developmental delays, with 66/74 (89%) being in Group 1 and 8/74 (11%) being in Group 2 (p \u3c 0.001). Motor developmental delays were predominant. The hip and knee muscular strength, according to the Medical Research Council (MRC) scale and the North Star Ambulatory Assessment (NSAA) activities, “standing on one leg R”, “standing on one leg L”, and “walk”, declined rapidly in Group 1 (p \u3c 0.001 In the follow-up analysis, Group 1 patients became wheelchair-bound at a younger age than those of Group 2 (p = 0.004). DMD motor dysfunction is linked to DMD mutations that affect shorter dystrophin isoforms. When stratifying individuals for clinical trials, considering the DMD mutation site and its impact on a shorter dystrophin isoform is crucial

Aerobic Composting using Sewage Sludge and Vegetable Waste

This Paper has made an attempt to study on changeability which happens in key parameters like pH, temperature, Carbon Nitrogen ratio, Total Nitrogen, Total Phosphorous, and Total Potassium during 80 days regular testing of composting procedure. A tremendous amount of vegetable waste produced in India. The transfer of vegetable waste alongside the municipal solid waste in landfills or dumpsite is making smell irritation, leachate creation into the climate. Composting of organic waste is the easy way to produce manure which can enhance physical, chemical and biological properties of soil. The vegetable waste is easily biodegradable and loaded with nutrients and organic material. For increasing nutrients amount of the waste sewage sludge will be added in proper proportion with vegetable waste. The sewage sludge will incorporate microbes to the vegetable waste to produce high nutrients manure. For this study, aerobic composting with the help of vegetable waste blended with sewage was done. The samples were analysed after every 10 days interval period to study various characteristics like pH, Temperature, Total Nitrogen, Total Phosphorus, Total Potassium, C/N ratio and Heavy Metal. Study indicated that composting can be an alternate technology for the management of sewage sludge disposal

Application of Dendrimer-based Nanoparticles in Glioma Imaging

Dendritic polymers or dendrimers present an alternate template for the development of nanoparticulate-based drug delivery and imaging systems. The smaller size (~7-12 nm) of dendrimers have the advantage over the other particles, because its smaller size can possibly improve tumor penetration and the inclusion of tumor specific drug release mechanisms. A Paramagnetic Chemical Exchange Saturation Transfer (PARACEST) MRI contrast agent, Eu-DOTA-Gly4 or a clinical relevant Gd-DOTA was conjugated on the surface of a G5 PAMAM dendrimer. To create a dual mode MRI-optical imaging nanoparticle, Dylight680 was also incorporated on the amines surface of a G5 dendrimer. The particle was detected with in vivo MRI in preclinical glioma animal model. Furthermore, noninvasive imaging results were validated with in vivo and ex-vivo optical imaging

TECHNOLOGY Plasma Gasification of Municipal Solid Waste: A Review

Utilization of plasma gasification in waste to energy is one of the novel applications meeting todays need for waste disposal. In this application, plasma arc, gasifies the carbon based part of waste materials such as municipal solid waste, sludge, agricultural waste, etc. and generating a synthetic gas which can be used to produce energy through engine generators, gas turbines and boilers. The non-carbon based part of the waste materials can be vitrified into glass and reusable metal. The analysis indicates that gasification is a technically viable option for the solid waste conversion, including residual waste from separate collection of municipal solid waste. The paper focuses on plasma gasification technology for waste disposal and energy generation with case study. It is able to meet existing emission limits and can have a remarkable effect on reduction of landfill disposal option

Biopiracy: Abolish Corporate Hijacking of Indigenous Medicinal Entities

Biopiracy as “a silent disease” is hardly detectable because it does not leave traces frequently. The corporate hijacking of food is the most important health hazard in this era; giant commercial enterprises are using intellectual property rights to patent indigenous medicinal plants, seeds, genetic resources, and traditional medicines. The new era of biotechnology relies on the genes of living organisms as raw materials. The “Gene Rush” has thus become similar to that of the old “Gold Rush.” Sri Lanka has been spotted in the top 34 biodiversity hotspots globally. Moreover, localized in the tropics, human generations in Sri Lanka have utilized the array of plant species for herbal treatments and treatment of diseases. Sri Lanka after its 30-year civil war is moving towards a solid growth and conservation of the environment which is a major component in a sustainable development where the conservation of biodiversity plays a significant role. In this paper, we present an overview of typical cases of global biopiracy, bioprospecting via introduction of cost-effective deoxyribonucleic acid (DNA) fingerprinting and international protocol with Private-Public-People Partnership concept as excellent forms of utilization of natural resources. We propose certain perspectives as scientists towards abolishing biopiracy and also to foster the fair utilization of natural resources; since the economy of most developing countries is agriculture based, the gross domestic product of the developing countries could be increased by enhanced bioprospecting via introduction of cost-effective DNA fingerprinting technologies and thus not being a pray of corporate hijacking.“Biopiracy is biological theft; illegal collection of indigenous plants by corporations who patent them for their own use” (Vandana Shiva)