Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

(E)-2-{[(2-Aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, ¹H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Automatic evaluation and data generation for analytical chemistry instrumental analysis exercises

In general, laboratory activities are costly in terms of time, space, and money. As such, the ability to provide realistically simulated laboratory data that enables students to practice data analysis techniques as a complementary activity would be expected to reduce these costs while opening up very interesting possibilities. In the present work, a novel methodology is presented for design of analytical chemistry instrumental analysis exercises that can be automatically personalized for each student and the results evaluated immediately. The proposed system provides each student with a different set of experimental data generated randomly while satisfying a set of constraints, rather than using data obtained from actual laboratory work. This allows the instructor to provide students with a set of practical problems to complement their regular laboratory work along with the corresponding feedback provided by the system's automatic evaluation process. To this end, the Goodle Grading Management System (GMS), an innovative web-based educational tool for automating the collection and assessment of practical exercises for engineering and scientific courses, was developed. The proposed methodology takes full advantage of the Goodle GMS fusion code architecture. The design of a particular exercise is provided ad hoc by the instructor and requires basic Matlab knowledge. The system has been employed with satisfactory results in several university courses. To demonstrate the automatic evaluation process, three exercises are presented in detail. The first exercise involves a linear regression analysis of data and the calculation of the quality parameters of an instrumental analysis method. The second and third exercises address two different comparison tests, a comparison test of the mean and a t-paired test.

AVOIDING FIRST-YEAR UNIVERSITY CHEMISTRY TEXTBOOKS’ MISREPRESENTATIONS IN THE TEACHING OF SPONTANEOUS REACTIONS

This paper summarizes the misrepresentations related to Gibbs energy in general chemistry textbooks. These misrepresentations arise from a problem in the terminology textbooks use. Thus, after reviewing the proper definition of each of the terms analyzed, we present two problems to exemplify the correct treatment of the quantities involved, which may help in the discussion and clarification of the misleading conventions and assumptions reported in this study.

INNOVATIVE USE OF A TABLET DEVICE TO DELIVER INSTRUCTION IN UNDERGRADUATE CHEMISTRY LECTURES

This report describes a simple, inexpensive and highly effective instructional model based on the use of a tablet device to enable the real-time projection of the instructor's digitally handwritten annotations to teach chemistry in undergraduate courses. The projection of digital handwriting allows the instructor to build, present and adapt the class contents in a dynamic fashion and to save anything that is annotated or displayed on the screen for subsequent sharing with students after each session. This method avoids the loss of continuity and information that often occurs when instructors switch between electronic slides and white/chalk board during lessons. Students acknowledged that this methodology allows them to follow the instructor's cognitive process and the progressive development of contents during lectures as the most valuable aspect of the implemented instructional model.

INTERAÇÕES FÁRMACO-RECEPTOR: APLICAÇÕES DE TÉCNICAS COMPUTACIONAIS EM AULA PRÁTICA SOBRE A EVOLUÇÃO DOS INIBIDORES DA ENZIMA CONVERSORA DE ANGIOTENSINA

Teaching classes and events regarding the molecular aspects of drug-receptor interactions is not an easy task. The ligand stereochemistry and the spatial arrangement of the macromolecular targets highly increase the complexity of the process. In this context, the use of alternative and more playful approaches could allow students to gain a more thorough understanding of this important topic in medicinal chemistry. Herein, we describe a practical teaching approach that uses computational strategies as a tool for drug-receptor interaction studies performed for angiotencsin converting enzyme inhibitors (ACEi). Firstly, the students learn how to find the crystallographic structure (enzyme-ligand complex). Then, they proceed to the treatment of crude crystallographic data. Thereafter, they learn how to analyze the positioning of the drug on the active site of the enzyme, looking for regions related to the molecular recognition. At the end of the study, students can summarize the molecular requirements for the interaction and the structure-activity relationships of the studied drugs.

INTERACTIONS: DESIGN, IMPLEMENTATION AND EVALUATION OF A COMPUTATIONAL TOOL FOR TEACHING INTERMOLECULAR FORCES IN HIGHER EDUCATION

Intermolecular forces are a useful concept that can explain the attraction between particulate matter as well as numerous phenomena in our lives such as viscosity, solubility, drug interactions, and dyeing of fibers. However, studies show that students have difficulty understanding this important concept, which has led us to develop a free educational software in English and Portuguese. The software can be used interactively by teachers and students, thus facilitating better understanding. Professors and students, both graduate and undergraduate, were questioned about the software quality and its intuitiveness of use, facility of navigation, and pedagogical application using a Likert scale. The results led to the conclusion that the developed computer application can be characterized as an auxiliary tool to assist teachers in their lectures and students in their learning process of intermolecular forces.

WOMAN IN CHEMISTRY. JANE MARCET, A RELEVANT FIGURE IN CHEMISTRY EDUCATION

A historiographical study of Jane Marcet’s role in spreading chemistry knowledge to a wider audience in the 19th century is presented here. Her efforts to spread scientific knowledge were crucial to sharing the most important theories of chemistry among different audiences, particularly women and young people. Through her book, “Conversations on Chemistry,” which was published in several editions from 1806 to 1853, she contributed significantly to chemistry education. Despite controversy over the large number of editions, this text is a strong witness to the active participation of women in science. Her scientific rigor and contribution to narrative strategies in chemistry pedagogy have given Jane Marcet consideration not only as an important woman in the scientific community of England during the first half of the 19th century but also as a central figure in the early development of chemistry diffusion and education.

AVALIAÇÃO DO USO DE PLANILHAS COMPUTACIONAIS COMO UMA FERRAMENTA DIDÁTICA EM QUÍMICA ANALÍTICA QUALITATIVA

The use of spreadsheet softwares is not widespread in Chemical Education in Brazil as a computational education tool. By its turn the Qualitative Analytical Chemistry is considered a discipline with classical and non-flexible content. Thus in this work the spreadsheet software Excel® was evaluated as a teaching tool in a Qualitative Analytical Chemistry course for calculations of concentrations of the species in equilibrium in solutions of acids. After presenting the theory involved in such calculations the students were invited to elaborate the representation of the distribution of these species in a graphical form, using the spreadsheet software. Then the teaching team evaluated the resulting graphics regarding form and contents. The graphics with conceptual and/or formal errors were returned for correction, revealing significant improvement in the second presentation in all cases. The software showed to be motivating for the content of the discipline, improving the learning interest, while it was possible to prove that even in classical disciplines it is possible to introduce new technologies to help the teaching process.

Computational visual quality of digitally printed images

The problem of understanding how humans perceive the quality of a reproduced image is of interest to researchers of many fields related to vision science and engineering: optics and material physics, image processing (compression and transfer), printing and media technology, and psychology. A measure for visual quality cannot be defined without ambiguity because it is ultimately the subjective opinion of an “end-user” observing the product. The purpose of this thesis is to devise computational methods to estimate the overall visual quality of prints, i.e. a numerical value that combines all the relevant attributes of the perceived image quality. The problem is limited to consider the perceived quality of printed photographs from the viewpoint of a consumer, and moreover, the study focuses only on digital printing methods, such as inkjet and electrophotography. The main contributions of this thesis are two novel methods to estimate the overall visual quality of prints. In the first method, the quality is computed as a visible difference between the reproduced image and the original digital (reference) image, which is assumed to have an ideal quality. The second method utilises instrumental print quality measures, such as colour densities, measured from printed technical test fields, and connects the instrumental measures to the overall quality via subjective attributes, i.e. attributes that directly contribute to the perceived quality, using a Bayesian network. Both approaches were evaluated and verified with real data, and shown to predict well the subjective evaluation results.

Computational Evaluation of Print Unevenness According to Human Vision

Print quality and the printability of paper are very important attributes when modern printing applications are considered. In prints containing images, high print quality is a basic requirement. Tone unevenness and non uniform glossiness of printed products are the most disturbing factors influencing overall print quality. These defects are caused by non ideal interactions of paper, ink and printing devices in high speed printing processes. Since print quality is a perceptive characteristic, the measurement of unevenness according to human vision is a significant problem. In this thesis, the mottling phenomenon is studied. Mottling is a printing defect characterized by a spotty, non uniform appearance in solid printed areas. Print mottle is usually the result of uneven ink lay down or non uniform ink absorption across the paper surface, especially visible in mid tone imagery or areas of uniform color, such as solids and continuous tone screen builds. By using existing knowledge on visual perception and known methods to quantify print tone variation, a new method for print unevenness evaluation is introduced. The method is compared to previous results in the field and is supported by psychometric experiments. Pilot studies are made to estimate the effect of optical paper characteristics prior to printing, on the unevenness of the printed area after printing. Instrumental methods for print unevenness evaluation have been compared and the results of the comparison indicate that the proposed method produces better results in terms of visual evaluation correspondence. The method has been successfully implemented as ail industrial application and is proved to be a reliable substitute to visual expertise.

Influence of topography and surface chemistry on the wetting properties of TiO2-based ceramic coatings

Vätning av fasta ytor är ett viktigt fenomen i såväl naturen som i en lång rad av industriella tillämpningar. Det är allmänt känt att vätningen av en fast yta styrs av ytans kemi samt struktur. Målsättningen med avhandlingen var att studera hur kemisk heterogenitet och ytråhet på nanometernivå påverkar vätningsegenskaperna hos en fast yta. Ytorna som studerades var titandioxid-baserade kerama ytor som framställdes med hjälp av en sol-gel process. Vätningstudierna utfördes genom kontaktvinkelmätningar, vilket innebär att man mäter vinkeln som vätska/luft-gränsskiktet hos en vätskedroppe bildar mot en fast yta. Ytråheten hos materialen studerades främst genom atomkraftsmikroskopi (AFM). I AFM detekteras ytans struktur av en mycket skarp nål som skannar ytan. Resultaten i avhandlingen kunde framgångsrikt modelleras med existerande teorier för vätning av heterogena ytor.