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Rhodamine derivatives have been found to sense transition metal ions selectively, and the related chemosensing behavior has been studied extensively. Drastic color changes and emission enhancements have been observed as a result of spirolactam ring-opening during the stimulation of certain transition metal ions. Because lanthanide ions are known to prefer higher coordination numbers than transition metal ions, the utilization of this preference is a potential strategy for exploring rhodamine-based chemosensors for selective lanthanide ion sensing. In addition to their application as chemosensors, rhodamine organic dyes can also be incorporated into luminescent transition metal systems and function as photosensitizers for efficient photodynamic therapy (PDT). Furthermore, introducing anti-cancer drugs into rhodamine-transition metal hybrid systems can yield synergistic effect that cause tumor cell death. In this thesis, we focus on the molecular design, characterization, properties, mechanisms, and practical application of rhodamine-based chemosensors and photosensitizers. In Chapter 1, the development of rhodamine-derivative-based chemosensors and rhodamine-containing transition metal complexes is summarized. In Chapter 2, a series of rhodamine-derivative-containing macrocycle compounds are designed, synthesized, and characterized. One macrocycle compound called MR1 was determined to exhibit selective sensing towards Tb( I) and Dy( I) ions with high sensitivity. Based on binding constants and high-resolution mass spectrometry measurement results, sensing mechanisms of MR1 for Tb( I) and Dy( I) ions are proposed. Furthermore, MR1 exhibits high stability and reusability for Ln( I) ion absorption in the solid state. This is the first example of rhodamine derivatives as fluorescent probes for Ln( I) ions. The molecular i structures of the macrocycle compounds are defined as follows: In Chapter 3, a series of rhodamine-appended Ir( I) complexes with different cyclometallating ligands are designed and synthesized, and the relationship between singlet oxygen (1O2) generation efficiency and the energy level of the Ir( I)-based triplet metal-to-ligand charge transfer (3MLCT) excited state (T1') is investigated and correlated. In addition to the direct population of the rhodamine triplet excited state (T1) through the intersystem crossing process, the T1' state acting as a relay could provide an additional pathway to generate the rhodamine T1 state, leading to enhanced 1O2 generation ability. More importantly, this study provides a novel concept for the molecular design and exploration of other photosensitizers for efficient PDT. The molecular structures of rhodamine-containing Ir( I) complexes are defined as follows: In Chapter 4, the mechanism proposed in Chapter 3 is verified to be adaptable not only in an iridium( I) system but also in a platinum( ) system. 1O2 generation ability is significantly enhanced by reducing the energy gap between the Pt( )-iv based 3MLCT state (T1') and rhodamine singlet state (S1). Furthermore, the in vitro PDT effect is significantly enhanced by introducing anti-cancer drugs into a rhodamine-tethered Pt( ) system. The molecular structures of Pt5 with high 1O2 generation ability and Pt6 with the best in vitro PDT performance are defined as follows:
This dissertation, "Design, Synthesis and Host-guest Chemistry of Rhodamine Derivatives and Their Transition Metal Complexes" by Ho-chuen, Lam, 林浩銓, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: New classes of luminescent transition metal complexes, including the systems of rhenium(I) tricarbonyl diimine, cyclometalated iridium(III) diimine, cyclometalated rhodium(III) diimine, ruthenium(II) diimine and ruthenium(II) terpyridine complexes tethered with rhodamine moieties, have been synthesized. The X-ray crystal structure of one of the cyclometalated rhodium(III) diimine complexes with rhodamine pendants, [Rh(SPLC2N2)(ppy)2](PF6) has been determined. The molecular structure of [Rh(SPLC2N2)(ppy)2](PF6) showed a distorted octahedral geometry and the rhodamine moiety was found in a spirolactam closed-ring form. All of them were found to exhibit emission in fluid solution. The emissions of rhenium(I) tricarbonyl diimine and ruthenium(II) polypyridyl complexes are derived from the triplet metal-to-ligand charge transfer (3MLCT) excited state, i.e. from dπ orbital of the rhenium(I) or ruthenium(II) metal center to the π* orbital of the diimine ligand; while that of cyclometalated iridium(III) diimine complexes is (3MLCT) [dπ(Ir) → π*(N DEGREESN)] and that of cyclometalated rhodium(III) diimine complexes involves the (3IL) [π → π*(N DEGREESC)] excited state, probably mixed with (3MLCT) [dπ(Rh) → π*(N DEGREESC)] character. The cation-binding properties of these complexes toward alkali, alkaline-earth and transition-metal cations were investigated by electronic absorption and emission spectrophotometries. Some of them were found to exhibit new low-energy absorption and emission bands, characteristic of the rhodamine absorption and emission, with high selectivity and sensitivity for certain transition metal cations. A series of rhodamine-appended Schiff base organic compounds has also been synthesized in order to explore their capability as luminescent lanthanide ion sensors. The lanthanide ion binding properties of one of the compounds in acetonitrile were examined. Upon addition of lanthanide ions, new intense low-energy electronic absorption and emission bands were also observed, characteristic of the rhodamine absorption and emission, demonstrating its lanthanide ion sensing behaviour. DOI: 10.5353/th_b5060562 Subjects: Rhodium compounds - Synthesis Transition metal complexes - Synthesis
The work contained within this thesis explores the synthetic strategies to several novel conjugated systems derived from porphyrin, NDI and TTF building blocks and their subsequent characterasation. These novel compounds have applicability in studying the factors that govern ET and EnT in interesting redox processes and as sensors. The bulk of research undertaken utilises the easy to prepare porphyrin-dione 44 and TTF 78 as well as tetrabromo NDI 19. Chapter 1 provides an introduction to the motivation for this research. The Chapter also summarises major directions in the fields of porphyrin, NDI and TTF chemistry and defines the significance and role of their properties as well as relevant applications.Chapter 2 explores the synthesis of novel porphyrinogens including oxidation of the porphyrin macrocycle. Core to the strategy is the porphyrin-dione 44. From this dione, porphyrin anhydride 57 and related metallo-porphyrins are synthesised and their physical properties explored. Obtaining porphyrin-lactone 58 as a side product during these reactions led us to synthesis novel lactams 62 and 63. Reaction of porphyrin-lactone 58 with hydrazine-hydrate converts the lactone moiety to an N-aminolactam 62. It also chemically reduces the antipodal pyrrolic moiety in the N-aminolactam, producing the chlorin-like N-aminochlorolactam 63 as well. This lactone-to-lactam replacement does not dramatically change the UV-visible spectroscopic properties of the N-aminolactam 62, however N-aminochlorolactam 63 shows intense Q band at 696 nm, which is larger than that of either of porphyrin-lactone 58 or N-amino-porpholactam 62, and is also shifted to the red region. Chapter 3 investigates the synthesis of novel porphyrin-TTF systems and their metal complexes. A tetrathiafulvalene donor has been annulated to 44 via quinoxaline linkers to form a novel asymmetric dyad 79. Chemical and physical properties are also outlined by utilising different methods such as UV-visible spectroscopy, fluorescence spectroscopy and cyclic voltammetry. These extended [pi]-conjugated molecules absorb light over a wide region of the UV-visible spectrum. Preliminary fluorescence testing of these compounds suggests that electron and/or energy transfer processes take place from the TTF unit as a donor to the porphyrin moiety as an acceptor. Also, cyclic voltametric studies allow the differentiate between the TTF and porphyrin sites with respect to the multiple redox processes occurring within these compounds. X-ray crystallography was used to characterise compound 79, adding to the structural information gained through other characterisation techniques.Chapter 4 investigates the synthesis of a new naphthalene diimide 104, in which a TTF donor has been attached to the naphthalene diimide core via a rigid bridge. The electronic properties of 104 are studied in detail. A strong electronic absorption profile extends far into the visible spectral region, which originates from its inherent electronic donor-acceptor nature. Also, the presence of a strong absorption at 1270 nm upon chemical oxidation, confirms significant [pi]-[pi] interactions in the compound due to aggregation.The work presented in Chapter 5 focused on synthesising of a novel 2,3-dipyrrol-2'-yl-TTF-quinoxaline 123, which is highly selective and sensitive for F- with detection possible by both colorimetric and fluorometric analyses. The target compound 123 was obtained via the direct condensation reaction of 78 with the 2,3-dipyrrol-2'-yl ethanedione 121 in good yield, and then characterized by various methods including X-ray crystallography. The UV-visible spectrum of 123 in DCM shows three strong absorption bands, which change after the addition of fluoride ion. Compound 123 also shows an emission intensity enhancement with slight red shift upon addition of F-, while no significant changes in the spectra of 123 was observed upon addition of AcO-, H2PO4-, Cl-, Br- and HSO4- in the same solvent. Chapter 6 reflects on the work undertaken in Chapters 2-5 and comments on future directions. It also describes some ancillary works to the main themes of this thesis. Synthesis of the NDI-TTF annulated compounds 126 and 127 under mild conditions are detailed, as well as dimer 128, which might have interesting photophysical properties. A new trimer 130 was also synthesised.
Lanthanides have fascinated scientists for more than two centuries now, and since efficient separation techniques were established roughly 50 years ago, they have increasingly found their way into industrial exploitation and our everyday lives. Numerous applications are based on their unique luminescent properties, which are highlighted in this volume. It presents established knowledge about the photophysical basics, relevant lanthanide probes or materials, and describes instrumentation-related aspects including chemical and physical sensors. The uses of lanthanides in bioanalysis and medicine are outlined, such as assays for in vitro diagnostics and research. All chapters were compiled by renowned scientists with a broad audience in mind, providing both beginners in the field and advanced researchers with comprehensive information on on the given subject.
The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.
An amphiphile is a molecule that contains a hydrophilic part and a hydrophobic part, linked by covalent bonding. Supramolecular amphiphiles (supra-amphiphiles) are amphiphiles linked by non-covalent interactions. As they employ non-covalent interactions, these species demonstrate adaptability and reversibility in conformational transformation, making them one of the most important emerging species in supramolecular chemistry. They have proven important in bridging the gap between molecular architecture and functional assembly. This book is written and edited by the current leaders in the topic and contains a foreword from Professor Jean-Marie Lehn, a father of the supramolecular chemistry field. Bringing together supramolecular chemistry and colloidal and interfacial science, the book provides a detailed and systematic introduction to supramolecular amphiphiles. Chapters explain how to employ non-covalent interactions to fabricate supra-amphiphiles. The book opens with an introduction to the history and development of the field, followed by chapters focussing on each type of interaction, including host-guest interaction, electrostatic interaction, charge-transfer interaction, hydrogen bonding and dynamic covalent bonds. This book will be a valuable resource for students new to this field and experienced researchers wanting to explore the wider context of their work.
Over the last three decades a lot of research on the role of metals in biochemistry and medicine has been done. As a result many structures of biomolecules with metals have been characterized and medicinal chemistry studied the effects of metal containing drugs. This new book (from the EIBC Book Series) covers recent advances made by top researchers in the field of metals in cells [the “metallome”] and include: regulated metal ion uptake and trafficking, sensing of metals within cells and across tissues, and identification of the vast cellular factors designed to orchestrate assembly of metal cofactor sites while minimizing toxic side reactions of metals. In addition, it features aspects of metals in disease, including the role of metals in neuro-degeneration, liver disease, and inflammation, as a way to highlight the detrimental effects of mishandling of metal trafficking and response to "foreign" metals. With the breadth of our recently acquired understanding of metals in cells, a book that features key aspects of cellular handling of inorganic elements is both timely and important. At this point in our understanding, it is worthwhile to step back and take an expansive view of how far our understanding has come, while also highlighting how much we still do not know. The content from this book will publish online, as part of EIBC in December 2013, find out more about the Encyclopedia of Inorganic and Bioinorganic Chemistry, the essential online resource for researchers and students working in all areas of inorganic and bioinorganic chemistry.
This book discusses the biological, technical and study-design challenges of Nanopharmaceuticals. Chapters of this book are dedicated to supermagentic iron oxide nanoparticles for the diagnosis of brain, breast, gastric, ovarian, liver, colorectal, lung and pancreatic cancers. It also includes a brief introduction to magnetic resonance imaging and ends with the future prospective of iron oxide nanoparticles in cancer detection. The book also provides a critical discussion on ‘Computational sequence design for DNA nanostructures’ and gives a brief introduction about the skin delivery. A detailed discussion has been included about the different types of nanocarriers such as micells, microemulsions, nanoemulsions, polymeric and lipid based nanoparticles. Focussing on the safety concerns of nanomedicine it also covers the safety issues, clinical benefits, ecotoxicity and regulatory frame work of nanopharmaceuticals.
Magnetic Resonance Imaging (MRI) is one of the most important tools in clinical diagnostics and biomedical research. The number of MRI scanners operating around the world is estimated to be approximately 20,000, and the development of contrast agents, currently used in about a third of the 50 million clinical MRI examinations performed every year, has largely contributed to this significant achievement. This completely revised and extended second edition: Includes new chapters on targeted, responsive, PARACEST and nanoparticle MRI contrast agents. Covers the basic chemistries, MR physics and the most important techniques used by chemists in the characterization of MRI agents from every angle from synthesis to safety considerations. Is written for all of those involved in the development and application of contrast agents in MRI. Presented in colour, it provides readers with true representation and easy interpretation of the images. A word from the Authors: Twelve years after the first edition published, we are convinced that the chemistry of MRI agents has a bright future. By assembling all important information on the design principles and functioning of magnetic resonance imaging probes, this book intends to be a useful tool for both experts and newcomers in the field. We hope that it helps inspire further work in order to create more efficient and specific imaging probes that will allow materializing the dream of seeing even deeper and better inside the living organisms. Reviews of the First Edition: "...attempts, for the first time, to review the whole spectrum of involved chemical disciplines in this technique..."—Journal of the American Chemical Society "...well balanced in its scope and attention to detail...a valuable addition to the library of MR scientists..."—NMR in Biomedicine
This comprehensive book presents the theoretical principles, current applications and latest research developments in the field of luminescent lanthanide complexes; a rapidly developing area of research which is attracting increasing interest amongst the scientific community. Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials begins with an introduction to the basic theoretical and practical aspects of lanthanide ion luminescence, and the spectroscopic techniques used to evaluate the efficiency of luminescence. Subsequent chapters introduce a variety of different applications including: • Circularly polarized luminescence • Luminescence bioimaging with lanthanide complexes • Two-photon absorption of lanthanide complexes • Chemosensors • Upconversion luminescence • Excitation spectroscopy • Heterometallic complexes containing lanthanides Each chapter presents a detailed introduction to the application, followed by a description of experimental techniques specific to the area and an extensive review of recent literature. This book is a valuable introduction to the literature for scientists new to the field, as well as providing the more experienced researcher with a comprehensive resource covering the most relevant information in the field; a ‘one stop shop’ for all key references.