Investigations of lysine and lysine-derived crosslinks in elastin via soild-state NMR spectroscopy

M.S

42nd Rocky Mountain Conference on Analytical Chemistry

Abstracts from the 42nd annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Broomfield, Colorado, July 30 - August 3, 2000

Structure and dynamics of biological and pharmaceutical systems by solid-state NMR: applications to complex materials and methodological developments on model systems

a) (Italiano) Questa tesi (redatta interamente in lingua inglese) descrive la caratterizzazione strutturale e dinamica di sistemi di interesse biologico e farmaceutico tramite l’applicazione di tecniche NMR a stato solido in alta e bassa risoluzione, nonché lo sviluppo di nuove metodologie NMR per lo studio di proprietà geometriche e dinamiche di sistemi solidi. Il lavoro presentato è suddiviso in 3 parti. La prima parte, che si articola in 3 capitoli, introduce i principi teorici alla base dell’NMR a stato solido (cap.1) e fornisce gli strumenti, sia teorici che sperimentali (cap. 2 e 3, rispettivamente), necessari al raggiungimento di una caratterizzazione dettagliata di campioni solidi. Nella seconda parte della tesi, che si articola in 4 capitoli, viene descritta l’applicazione di tali strumenti alla caratterizzazione di 4 esempi di campioni di interesse biologico o farmaceutico. In particolare, il cap. 4 descrive la caratterizzazione della formulazione finale costituita dal farmaco anti-infiammatorio-non-steroideo Flurbiprofen disperso nella matrice polimerica costituita dal carrier Eudragit RL100; nel cap. 5 viene presentata la caratterizzazione morfologico-dinamica di un sistema per il rilascio controllato di farmaci poco solubili costituito da N-carbossimetilchitosano; il cap. 6 descrive lo studio degli effetti indotti da un diverso grado di invecchiamento artificiale su campioni di farine; il cap. 7 presenta la caratterizzazione delle proprietà morfologiche e dinamiche di sistemi biocompositi costituiti da fibre di cotone incapsulate con copolimeri di etilacrilato e stirene. La terza parte della tesi, che si articola in 2 capitoli, descrive due metodologie NMR a stato solido sviluppate durante gli studi di dottorato. Il cap. 8 introduce e descrive un metodo per la caratterizzazione dinamica di sistemi polimerici amorfi tramite un’analisi globale di tempi di rilassamento spin-reticolo. Il cap. 9, infine, descrive lo sviluppo e l’applicazione di una sequenza di impulsi NMR per la determinazione di distanze internucleari in sistemi multispin in fase solida. Il corpo della tesi, qui descritto, è integrato da 3 appendici (A, B, C), introduzione e conclusioni, nonché dalle introduzioni alle parti 2 e 3. b) (English) This Thesis concerns the structural and dynamic characterization of systems of biological and pharmaceutical interest by means of solid-state NMR, as well as the development of new NMR methodologies for the study of the geometrical and dynamic properties of solid systems. The work is divided into three parts. The first part, articulated in three chapters, introduces the thoretical principles at the basis of solid-state NMR (chap. 1) and the tools, either theoretical or experimental (chap. 2 and 3, respectively), necessary for the achievement of a detailed characterization of solid samples. The second part of the Thesis, divided into 4 chapters, describes the application of such tools to the characterization of 4 examples of solid samples of either biological or pharmaceutical interest. In particular, chap. 4 deals with the study of a drug final formulation composed of the non-steroidal-anti-inflammatory drug Flurbiprofen with the polymeric carrier Eudragit RL100; chap. 5 presents the morphological and dynamic characterization of a sustained-release systems apt at the transport and site-specific release of poorly soluble drugs in the gastro-intestinal tract constituted by N-carboxymethyl-chitosan; chap. 6 describes the solid-state NMR characterization of flours at different accelerated aging degrees; chap. 7 deals with the characterization of natural-fiber reinforced composites obtained through the encapsulation of cotton fibers with synthetic copolymers. The third part of the Thesis, articulated in two chapters, describes two solid-state NMR methodologies developed during the PhD studies. In particular, chap. 8 introduces and describes a method for the dynamic characterization of amorphous polymeric systems by means of a global analysis of spin-lattice relaxation times; finally, chap. 9 describes the development and the application of a solid-state NMR pulse sequence for the determination of internuclear distances in multiple spin systems. The body of the Thesis, described above, is completed by 3 appendices (A, B and C), introduction, conclusions, as well as the introductions to Part 2 and 3

In situ High Pressure and Temperature 13C NMR for the Study of Carbonation Reactions of CO2

The aqueous reactions of carbon dioxide with various Mg-containing minerals [MgO, Mg(OH)2, and Mg2SiO4] at several different pressures: 1-200 bar) and temperatures: 25-150C) have been studied using a novel, elevated pressure and temperature 13C NMR probe. Critical observations about reaction rates, chemical exchange, and pH measurements throughout these reactions and the implications of the in situ measurements made during these reactions are discussed. A new method is used to elucidate pH under high pressure and temperature conditions which utilizes a calculation scheme wherein experimental data and a computational model are combined. Additionally, a 1D pH imaging method is employed to observe pH gradient effects across mineral samples during their reaction with CO2. Finally, other experimental details are discussed including ex situ analysis on carbonate products using pXRD, Raman, and MAS NMR. Detailed discussion outlines how to use 13C NMR to study CO2 mineralization reactions

43rd Rocky Mountain Conference on Analytical Chemistry

Final program, abstracts, and information about the 43rd annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 29 - August 2, 2001

On the Rationalization of the Formation, Stability and Phase Transitions of Pharmaceutically Active Solid Substance Solvates

Elektroniskā versija nesatur pielikumusŠajā disertācijā farmaceitiski aktīvo vielu veidoto solvātu un polimorfu analīze, solvātu stabilitāte un fāžu pārejas ir izmantotas, lai tuvotos situācijai, kad, izmantojot kristāliskās struktūras informāciju, būtu iespējams pilnībā izprast un racionalizēt solvātu veidošanās virzītājspēkus, to stabilitāti un desolvatācijas mehānismu. Analizējot mildronāta dihidrāta dehidratācijas procesu un kinētiku, noskaidrots tā dehidratācijas mehānisms. Lietojot molekulāro īpašību, kristālisko struktūru un kvantu aprēķinu rezultātu analīzi, racionalizēta droperidola un benperidola solvātu veidošanās, stabilitāte un fāžu pārejas. Lai atrastu rīku solvātu termiskās stabilitātes racionalizēšanai, kā arī skaidrotu novēroto atšķirīgo šķīdinātāja molekulu novietojumu un dinamiku kristāliskajās struktūrās, ir pētīti droperidola izostrukturālie solvāti.In this doctoral thesis analysis of the solvate and polymorph landscape, solvate stability and phase transitions of active pharmaceutical ingredients are used to approach a possibility where the crystal structures could be used to completely understand and rationalize driving forces for solvate formation, stability and desolvation mechanism. A study of the dehydration of mildronate dihydrate is used to rationalize its dehydration mechanism. Solvate formation, stability and phase transitions of droperidol and benperidol is rationalized using analysis of molecular properties, crystal structures and computational calculations. Droperidol isostructural solvates are used to find a tool for rationalization of solvate thermal stability and explain the observed different solvent molecule arrangement and dynamics in their crystal structures

Molecular level understanding of supramolecular gels

Supramolecular gels are complex materials which have an expanding scope of industrial and biomedical applications, due to their unique viscoelastic properties, high biocompatibility and possibility of functionalisation. The hierarchical structure of molecular materials combines domains with drastically different degrees of ordering and molecular mobility. This makes their full characterisation a significant methodological and experimental challenge. The focus of this work was therefore the understanding of a variety of supramolecular semicrystalline gels in which very rigid solid components coexist with a dynamic and highly mobile solution phase. Using the examples of amino acid and urea-derivatives gelators, control of the self-assembly processes was successfully gained and tuning of the mechanical properties of the resulting materials by incorporating molecular structure modifications or introducing a variety of structurally diverse additives was achieved. Modification of the structure of the gel fibres was observed, which modulated the dynamic properties of the gel/solution interfaces and dictated the overall behaviour of the system, an aspect which is not commonly investigated in molecular gels. The resulting single and multi-component gels were used as model materials for the development of an NMR-based general strategy capable of probing the several hierarchical levels present. The multiphasic character of molecular gels required the combined use of solid, solution-state and HR-MAS NMR methods. This project has expanded the understanding of saturation transfer difference NMR experiments, with special focus in their applicability and limitations for the study of supramolecular soft systems. This approach was validated using complementary techniques, more specifically, rheology, microscopy, X-ray diffraction and computational methods. By combining molecular level understanding and measurements of the bulk properties, a methodology which can be applied to other soft materials used in pharmaceutical, biomedical and food science applications was developed. Moreover, this approach might have a generic impact in different fields of science and technology, enabling one to direct the recognition and host-guest properties of soft solids, which is essential for their targeted applications

Preclinical MRI of the Kidney

This Open Access volume provides readers with an open access protocol collection and wide-ranging recommendations for preclinical renal MRI used in translational research. The chapters in this book are interdisciplinary in nature and bridge the gaps between physics, physiology, and medicine. They are designed to enhance training in renal MRI sciences and improve the reproducibility of renal imaging research. Chapters provide guidance for exploring, using and developing small animal renal MRI in your laboratory as a unique tool for advanced in vivo phenotyping, diagnostic imaging, and research into potential new therapies. Written in the highly successful Methods in Molecular Biology series format, chapters include introductions to their respective topics, lists of the necessary materials and reagents, step-by-step, readily reproducible laboratory protocols, and tips on troubleshooting and avoiding known pitfalls. Cutting-edge and thorough, Preclinical MRI of the Kidney: Methods and Protocols is a valuable resource and will be of importance to anyone interested in the preclinical aspect of renal and cardiorenal diseases in the fields of physiology, nephrology, radiology, and cardiology. This publication is based upon work from COST Action PARENCHIMA, supported by European Cooperation in Science and Technology (COST). COST (www.cost.eu) is a funding agency for research and innovation networks. COST Actions help connect research initiatives across Europe and enable scientists to grow their ideas by sharing them with their peers. This boosts their research, career and innovation. PARENCHIMA (renalmri.org) is a community-driven Action in the COST program of the European Union, which unites more than 200 experts in renal MRI from 30 countries with the aim to improve the reproducibility and standardization of renal MRI biomarkers

Review of Particle Physics

The Review summarizes much of particle physics and cosmology. Using data from previous editions, plus 2,143 new measurements from 709 papers, we list, evaluate, and average measured properties of gauge bosons and the recently discovered Higgs boson, leptons, quarks, mesons, and baryons. We summarize searches for hypothetical particles such as supersymmetric particles, heavy bosons, axions, dark photons, etc. Particle properties and search limits are listed in Summary Tables. We give numerous tables, figures, formulae, and reviews of topics such as Higgs Boson Physics, Supersymmetry, Grand Unified Theories, Neutrino Mixing, Dark Energy, Dark Matter, Cosmology, Particle Detectors, Colliders, Probability and Statistics. Among the 120 reviews are many that are new or heavily revised, including a new review on Machine Learning, and one on Spectroscopy of Light Meson Resonances. The Review is divided into two volumes. Volume 1 includes the Summary Tables and 97 review articles. Volume 2 consists of the Particle Listings and contains also 23 reviews that address specific aspects of the data presented in the Listings