948 resultados para metal-directed self-assembling


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Most drugs function by binding reversibly to specific biological targets, and therapeutic effects generally require saturation of these targets. One means of decreasing required drug concentrations is incorporation of reactive metal centers that elicit irreversible modification of targets. A common approach has been the design of artificial proteases/nucleases containing metal centers capable of hydrolyzing targeted proteins or nucleic acids. However, these hydrolytic catalysts typically provide relatively low rate constants for target inactivation. Recently, various catalysts were synthesized that use oxidative mechanisms to selectively cleave/inactivate therapeutic targets, including HIV RRE RNA or angiotensin converting enzyme (ACE). These oxidative mechanisms, which typically involve reactive oxygen species (ROS), provide access to comparatively high rate constants for target inactivation. Target-binding affinity, co-reactant selectivity, reduction potential, coordination unsaturation, ROS products (metal-associated vsmetal-dissociated; hydroxyl vs superoxide), and multiple-turnover redox chemistry were studied for each catalyst, and these parameters were related to the efficiency, selectivity, and mechanism(s) of inactivation/cleavage of the corresponding target for each catalyst. Important factors for future oxidative catalyst development are 1) positioning of catalyst reduction potential and redox reactivity to match the physiological environment of use, 2) maintenance of catalyst stability by use of chelates with either high denticity or other means of stabilization, such as the square planar geometric stabilization of Ni- and Cu-ATCUN complexes, 3) optimal rate of inactivation of targets relative to the rate of generation of diffusible ROS, 4) targeting and linker domains that afford better control of catalyst orientation, and 5) general bio-availability and drug delivery requirements.

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The context of this study is corporate e-learning, with an explicit focus on how digital learning design can facilitate self-regulated learning (SRL). The field of e-learning is growing rapidly. An increasing number of corporations use digital technology and elearning for training their work force and customers. E-learning may offer economic benefits, as well as opportunities for interaction and communication that traditional teaching cannot provide. However, the evolving variety of digital learning contexts makes new demands on learners, requiring them to develop strategies to adapt and cope with novel learning tools. This study derives from the need to learn more about learning experiences in digital contexts in order to be able to design these properly for learning. The research question targets how the design of an e-learning course influences participants’ self-regulated learning actions and intentions. SRL involves learners’ ability to exercise agency in their learning. Micro-level SRL processes were targeted by exploring behaviour, cognition, and affect/motivation in relation to the design of the digital context. Two iterations of an e-learning course were tested on two groups of participants (N=17). However, the exploration of SRL extends beyond the educational design research perspective of comparing the effects of the changes to the course designs. The study was conducted in a laboratory with each participant individually. Multiple types of data were collected. However, the results presented in this thesis are based on screen observations (including eye tracking) and video-stimulated recall interviews. These data were integrated in order to achieve a broad perspective on SRL. The most essential change evident in the second course iteration was the addition of feedback during practice and the final test. Without feedback on actions there was an observable difference between those who were instruction-directed and those who were self-directed in manipulating the context and, thus, persisted whenever faced with problems. In the second course iteration, including the feedback, this kind of difference was not found. Feedback provided the tipping point for participants to regulate their learning by identifying their knowledge gaps and to explore the learning context in a targeted manner. Furthermore, the course content was consistently seen from a pragmatic perspective, which influenced the participants’ choice of actions, showing that real life relevance is an important need of corporate learners. This also relates to assessment and the consideration of its purpose in relation to participants’ work situation. The rigidity of the multiple choice questions, focusing on the memorisation of details, influenced the participants to adapt to an approach for surface learning. It also caused frustration in cases where the participants’ epistemic beliefs were incompatible with this kind of assessment style. Triggers of positive and negative emotions could be categorized into four levels: personal factors, instructional design of content, interface design of context, and technical solution. In summary, the key design choices for creating a positive learning experience involve feedback, flexibility, functionality, fun, and freedom. The design of the context impacts regulation of behaviour, cognition, as well as affect and motivation. The learners’ awareness of these areas of regulation in relation to learning in a specific context is their ability for design-based epistemic metareflection. I describe this metareflection as knowing how to manipulate the context behaviourally for maximum learning, being metacognitively aware of one’s learning process, and being aware of how emotions can be regulated to maintain volitional control of the learning situation. Attention needs to be paid to how the design of a digital learning context supports learners’ metareflective development as digital learners. Every digital context has its own affordances and constraints, which influence the possibilities for micro-level SRL processes. Empowering learners in developing their ability for design-based epistemic metareflection is, therefore, essential for building their digital literacy in relation to these affordances and constraints. It was evident that the implementation of e-learning in the workplace is not unproblematic and needs new ways of thinking about learning and how we create learning spaces. Digital contexts bring a new culture of learning that demands attitude change in how we value knowledge, measure it, define who owns it, and who creates it. Based on the results, I argue that digital solutions for corporate learning ought to be built as an integrated system that facilitates socio-cultural connectivism within the corporation. The focus needs to shift from designing static e-learning material to managing networks of social meaning negotiation as part of a holistic corporate learning ecology.

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Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

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For advanced devices in the application fields of data storage, solar cell and biosensing, one of the major challenges to achieve high efficiency is the fabrication of nanopatterned metal oxide surfaces. Such surfaces often require both precise structure at the nanometer scale and controllable patterned structure at the macro scale. Nowadays, the dominating candidates to fabricate nanopatterned surfaces are the lithographic technique and block-copolymer masks, most of which are unfortunately costly and inefficient. An alternative bottom-up approach, which involves organic/inorganic self-assembly and dip-coating deposition, has been studied intensively in recent years and has proven to be an effective technique for the fabrication of nanoperforated metal oxide thin films. The overall objective of this work was to optimize the synthesis conditions of nanoperforated TiO2 (NP-TiO2) thin films, especially to be compatible with mixed metal oxide systems. Another goal was to develop fabrication and processing of NP-TiO2 thin films towards largescale production and seek new applications for solar cells and biosensing. Besides the traditional dip-coating and drop-casting methods, inkjet printing was used to prepare thin films of metal oxides, with the advantage of depositing the ink onto target areas, further enabling cost-effective fabrication of micro-patterned nanoperforated metal oxide thin films. The films were characterized by water contact angle determination, Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Grazing Incidence XRay Diffraction. In this study, well-ordered zinc titanate nanoperforated thin films with different Zn/Ti ratios were produced successfully with zinc precursor content up to 50 mol%, and the dominating phase was Zn2Ti3O8. NP-TiO2 structures were also obtained by a cost-efficient means, namely inkjet printing, at both ambient temperature and 60 °C. To further explore new biosensing applications of nanoperforated oxide thin films, inkjet printing was used for the fabrication of both continuous and patterned polymeric films onto NP-TiO2 and perfluorinated phosphate functionalized NP-TiO2 substrates, respectively. The NP-TiO2 films can be also functionalized with a fluoroalkylsilane, resulting in hydrophobic surfaces on both titania and silica. The surface energy contrast in the nanoperforations can be tuned by irradiating the films with UV light, which provides ideal model systems for wettability studies.

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The new Physiotherapy and Occupational Therapy programmes, based in the Faculty of Health Sciences, McMaster University (Hamilton, Ontario) are unique. The teaching and learning philosophies utilized are based on learner-centred and selfdirected learning theories. The 1991 admissions process of these programmes attempted to select individuals who would make highly qualified professionals and who would have the necessary skills to complete such unique programmes. In order to: 1 . learn more about the concept of self-directed learning and its related characteristics in health care professionals; 2. examine the relationship between various student characteristics - personal, learner and those assessed during the admissions process - and final course grades, and 3. determine which, if any, smdent characteristics could be considered predictors for success in learner-centred programmes requiring self-directed learning skills, a correlational research design was developed and carried out. Thirty Occupational Therapy and thirty Physiotherapy smdents were asked to complete 2 instruments - a questionnaire developed by the author and the Oddi Continuing Learning Inventory (Oddi, 1986). Course grades and ratings of students during the admissions process were also obtained. Both questionnaires were examined for reliability, and factor analyses were conducted to determine construct validity. Data obtained from the questionnaires, course grades and student ratings (from the admissions process) were analyzed and compared using the Contingency Co-efficient, the Pearson's product-moment correlation co-efficient, and the multiple regression analysis model. The research findings demonstrated a positive relationship (as identified by Contingency Coefficient or Pearson r values) between various course grades and the following personal and learner characteristics: field of smdy of highest level of education achieved, level of education achieved, sex, marital stams, motivation for completing the programmes, reasons for eru-oling in the programmes, decision to enrol in the programmes, employment history, preferred learning style, strong selfconcept and the identification of various components of the concept of self-directed learning. In most cases, the relationships were significant to the 0.01 or 0.(X)1 levels. Results of the multiple regression analyses demonstrated that several learner and admissions characteristic variables had R^ values that accounted for the largest proportion of the variance in several dependent variables. Thus, these variables could be considered predictors for success. The learner characteristics included: level of education and strong self-concept. The admissions characteristics included: ability to evaluate strengths, ability to give feedback, curiosity and creativity, and communication skills. It is recommended that research continue to be conducted to substantiate the relationships found between course grades and characteristic variables in more diverse populations. "Success in self-directed programmes" from the learner's perspective should also be investigated. The Oddi Continuing Learning Inventory should continue to be researched. Further research may lead to refinement or further development of the instrument, and may provide further insight into self-directed learner attributes. The concept of self-directed learning continues to be incorporated into educational programmes, and thus should continue to be explored.

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The intent in this study was to investigate in what ways teachers· beliefs about education and teaching are expressed in the specific teaching behaviours they employ, and whether teaching behaviours, as perceived by their students, are correlated with students· critical thinking and self-directed learning. To this end the relationships studied were: among faCUlty members· philosophy of teaching, locus of control orientation, psychological type, and observed teaching behaviour; and among students· psychological type, perceptions of teaching behaviour, self-directed learning readiness, and critical thinking. The overall purpose of the study was to investigate whether the implicit goals of higher education, critical thinking and self-direction, were actually accounted for in the university classroom. The research was set within the context of path-goal theory, adapted from the leadership literature. Within this framework, Mezirow·s work on transformative learning, including the influences of Habermas· writings, was integrated to develop a theoretical perspective upon which to base the research methodology. Both qualitative and quantitative methodologies were incorporated. Four faCUlty and a total of 142 students participated in the study. Philosophy of teaching was described through faCUlty interviews and completion of a repertory grid. Faculty completed a descriptive locus of control scale, and a psychological type test. Observations of their teaching behaviour were conducted. Students completed a Teaching Behaviour Assessment Scale, the Self-Directed Learning Readiness Scale, a psychological type test, and the Watson-Glaser Critical Thinking Appraisal. A small sample of students were interviewed. Follow-up discussions with faculty were used to validate the interview, observation, teaching behaviour, and repertory grid data. Results indicated that some discrepancies existed between faculty's espoused philosophy of teaching and their observed teaching behaviour. Instructors' teaching behaviour, however, was a function of their personal theory of practice. Relationships were found between perceived teaching behaviour and students· self-directed learning and critical thinking, but these varied across situations, as would be predicted from path-goal theory. Psychological type of students and instructor also accounted for some of the variability in the relationships studied. Student psychological type could be shown as a partial predictor of self-directed learning readiness. The results were discussed in terms of theory development and implications for further research and practice.

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This qualitative study examined the perceived thoughts, feelings and experiences of seven public health nurses employed in a southern ontario health department, regarding the initial phase of the introduction of a self-directed orientation program in their place of employment. A desire to understand what factors facilitate public health nurses in the process of becoming self-directed learners was the purpose of this study. Data were gathered by three methods: 1) a standard open-ended interview was conducted by the researcher with each nurse for approximately one hour; 2) personal notes were kept by the researcher throughout the study; and 3) a review of all pertinent health department documents such as typed minutes of meetings and memos which referred to the introduction of the self-directed learning model was conducted. The meaning of the experience for the nurses provided some insights into what does and does not facilitate public health nurses in the process of becoming self-directed learners. Implications and recommendations for program planners, nurse administrators, facilitators of learning and researchers evolved from the findings of this study.

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A significant number of adults in adult literacy programs in Ontario have specific learning difficulties. This study sought to examine the holistic factors that contributed to these learners achieving their goals. Through a case study design, the data revealed that a combination of specific learning methods and strategies, along with particular characteristics of the instructor, participant, and class, and the evidence of self-transformation all seemed to contribute to the participant's success in the program. Instructor-directed teaching and cooperative learning were the main learning methods used in the class. General learning strategies employed were the use of core curriculum and authentic documents, and using phonics, repetition, assistive resources, and using activities that appealed to various learning styles. The instructor had a history of both professional development in the area of learning disabilities as well as experience working with learners who had specific learning difficulties. There also seemed to be a goodness of fit between the participant and the instructor. Several characteristics of the participant seemed to aid in his success: his positive self-esteem, self-advocacy skills, self-determination, self-awareness, and the fact that he enjoyed learning. The size (3-5 people) and type of class (small group) also seemed to have an impact. Finally, evidence that the participant went through a self-transformation seemed to contribute to a positive learner identity. These results have implications for practice, theory, and further research in adult education.

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Interventions using applied behaviour analysis (ABA) are widely used with children with autism spectrum disorders (ASD). Individuals who work with this population are important to target for ABA education. This study evaluated the efficacy of a self-directed program in increasing parent and student ABA knowledge and skills, self-efficacy, and new skill development in children with ASD. Study 1 was a pilot study of the newly developed evaluation materials. Study 2 tested the self-instructional package with three parents of children with ASD, three university students, and eight children diagnosed with ASD. Parents and students were given the Simple Steps ABA training package to use independently and were measured using a multiple baseline across participants and/or skills design. After training, ABA knowledge scores and self-efficacy showed variable improvement as did children’s appropriate behaviours. These results suggest that more research is needed to determine the efficacy of a self-instructional ABA package.

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The purpose of the study was to investigate whether teaching inactive and low active women to use mirrors for form and technique purposes could lessen the negative impact of mirrors on self-presentational concerns, affect, and self-efficacy. Eligible women (N = 82) underwent a one-on-one weight training orientation with a personal trainer. Participants were randomized into one of four experimental groups, each unique in the type of feedback (general or technique-specific) and the degree of focus on the mirror for technique reinforcement. Questionnaires assessed study outcomes pre- and post-orientation. Results indicated groups did not significantly differ on any post-condition variables, when controlling for pre-condition values (all p’s >.05). All groups showed outcome improvements following the orientation. This suggests that during a complex task, a personal trainer who emphasizes form and technique can facilitate improvements to psychological outcomes in novice exercisers, independent of the presence of mirrors or directional cues provided.

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La polyvalence de la réaction de couplage-croisé C-N a été explorée pour la synthèse de deux nouvelles classes de ligands: (i) des ligands bidentates neutres de type N^N et (ii) des ligands tridentates neutres de type N^N^N. Ces classes de ligands contiennent des N-hétérocycles aromatiques saturés qui sont couplés avec hexahydropyrimidopyrimidine (hpp). Les ligands forment de cycles à six chaînons sur la coordination du centre Ru(II). Ce fait est avantageux pour améliorer les propriétés photophysiques des complexes de polypyridyl de Ru(II). Les complexes de Ru(II) avec des ligands bidentés ont des émissions qui dépendent de la basicité relative des N-hétérocycles. Bien que ces complexes sont électrochimiquement et photophysiquement attrayant, le problème de la stereopurité ne peut être évité. Une conception soigneuse du type de ligand nous permet de synthétiser un ligand bis-bidentate qui est utile pour surmonter le problème de stereopurité. En raison de la spécialité du ligand bis-bidentate, son complexe diruthénium(II,II) présente une grande diastéréosélectivité sans séparation chirale. Alors que l'unité de hpp agit comme un nucléophile dans le mécanisme de C-N réaction de couplage croisé, il peut également agir en tant que groupe partant, lorsqu'il est activé avec un complexe de monoruthenium. Les complexes achiraux de Ru(II) avec les ligands tridentés présentent des meilleures propriétés photophysiques en comparason avec les prototypes [Ru(tpy)2]2+ (tpy = 2,2′: 6′, 2′′-terpyridine). L’introduction de deux unités de hpp dans les ligands tridentates rend le complexe de Ru(II) en tant que ‘absorbeur noir’ et comme ‘NIR émetteur’ (NIR = de l’anglais, Near Infra-Red). Cet effet est une conséquence d'une meilleure géométrie de coordination octaédrique autour de l'ion Ru(II) et de la forte donation sigma des unités hpp. Les complexes du Re(I) avec des ligands tridentates présentent un comportement redox intéressant et ils émettent dans le bleu. L'oxydation quasi-réversible du métal est contrôlée par la donation sigma des fragments hpp, tandis que la réduction du ligand est régie par la nature électronique du motif N-hétérocycle central du ligand lui-même. Cette thèse presente également l'auto-assemblage des métal-chromophores comme ‘métallo-ligands’ pour former des espèces supramoléculaires discretes utilisant des complexes neutres. Les synthèses et propriétés des métaux-chromophores précités et les supramolécules sont discutées.

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A novel N4O coordination mode offers carbohydrazone ligands as a building block for interesting frameworks through self-assembly. Bridging mode of oxygen of bis(2-benzoylpyridine ketone) carbohydrazone (H2L) with metal centers facilitates the formation of the macrocyclic molecular square [Zn(HL)]4(BF4)4 · 10H2O, offers wide range of applications for carbohydrazones.

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Self- and cross-velocity correlation functions and related transport coefficients of molten salts are studied by molecular-dynamics simulation. Six representative systems are considered, i.e., NaCl and KCl alkali halides, CuCl and CuBr noble-metal halides, and SrCl2 and ZnCl2 divalent metal-ion halides. Computer simulation results are compared with experimental self-diffusion coefficients and electrical conductivities. Special attention is paid to dynamic cross correlations and their dependence on the Coulomb interactions as well as on the size and mass differences between anions and cations.

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Supra molecular architectures of coordination complexes of liydrazones through non covalent interactions have been explored. Molecular self—assernbly driven by weak interactions such as hydrogen— bonding, K '”T[, C-1-I‘ "TE, van der Waals interactions, and so forth are currently of tremendous research interest in the fields of molecule based materials. The directional properties of the hydrogembonding interaction associate discrete molecules into aggregate structures that are sufficiently stable to be considered as independent chemical species. Chemistry can borrow nature’s strategy to utilize hydrogen-bonding as Well as other noncovalent interactions as found in secondary and tertiary structures of proteins such as the double helix folding of DNA, hydrophobic selflorganization of phospholipids in cell membrane etc. In supramolecular chemistry hydrogen bonding plays an important role in forming a variety of architectures. Thus, the wise modulation and tuning of the complementary sites responsible for hydrogen—bond formation have led to its application in supramolecular electronics, host-guest chemistry, self-assembly of molecular capsules, nanotubes etc. The work presented in this thesis describes the synthesis and characterization of metal complexes derived from some substituted aroylhydrazones. The thesis is divided into seven chapters.

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The heavy metal contamination in the environment may lead to circumstances like bioaccumulation and inturn biomagnification. Hence cheaper and effective technologies are needed to protect the precious natural resources and biological lives. A suitable technique is the one which meets the technical and environmental criteria for dealing with a particular remediation problem and should be site-specific due to spatial and climatic variations and it may not economically feasible everywhere. The search for newer technologies for the environmental therapy, involving the removal of toxic metals from wastewaters has directed attention to adsorption, based on metal binding capacities of various adsorbent materials. Therefore, the present study aim to identify and evaluate the most current mathematical formulations describing sorption processes. Although vast amount of research has been carried out in the area of metal removal by adsorption process using activated carbon few specific research data are available in different scientific institutions. The present work highlights the seasonal and spatial variations in the distribution of some selected heavy metals among various geochemical phases of Cochin Estuarine system and also looked into an environmental theraptic/remedial approach by adsorption technique using activated charcoal and chitosan, to reduce and thereby controlling metallic pollution. The thesis has been addressed in seven chapters with further subdivisions. The first chapter is introductory, stating the necessity of reducing or preventing water pollution due to the hazardous impact on environment and health of living organisms and drawing it from a careful review of literature relevant to the present study. It provides a constricted description about the study area, geology, and general hydrology and also bears the major objectives and scope of the present study.