Orientador: Luis Vicente de Andrade Scalvi / Resumo: A proposta deste trabalho é a investigação e compreensão de propriedades ópticas e eletrônicas da heteroestrutura formada pelo semicondutor III-V GaAs e o semicondutor óxido SnO2. A deposição de filmes finos de GaAs é feita por evaporação resistiva, e a de filmes finos de SnO2 dopados com o íon terra-rara Eu3+ pelo processo sol-gel-dip-coating, combinando um material semicondutor com alta mobilidade eletrônica e transição direta (GaAs), com semicondutor de bandgap largo (SnO2) e condutividade naturalmente do tipo-n, onde a emissão de Eu3+ é bastante eficiente. Amostras desses dois materiais foram investigadas preliminarmente de forma separada, como filmes finos, ou pós de SnO2:Eu prensados na forma de pastilhas. Fotoluminescência foi medida em heteroestruturas GaAs/SnO2:2%Eu com tratamentos térmicos em baixa temperatura (200 e 400°C), enquanto filmes de SnO2:2%Eu isolados apenas apresentaram picos de emissão do Eu3+ quando tratados com temperatura elevada (1000°C), porém com baixa intensidade. A hipótese para esse fenômeno foi associada com aglomerados de Eu3+ na superfície das amostras. Medidas de XAFS têm possibilitado o estudo da incorporação do dopante Eu na matriz SnO2, e na compreensão do mecanismo da luminescência encontrada. Análises de XANES mostraram que o átomo de európio permanece no estado de oxidação trivalente após a síntese da solução e tratamentos térmicos feitos, e que a heteroestrutura apresenta menos distorção na rede e estrutura mais ordenada quando compa... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The purpose of this work is the investigation and comprehension of optical and electronic properties of the heterostructure, formed by the III-V semiconductor GaAs and the oxide semiconductor SnO2. The deposition of GaAs thin films is accomplished by the resistive evaporation technique, and thin films of SnO2, doped with the rare earth ion Eu3+, by the sol-gel-dip-coating process, combining a semiconductor material with high electronic mobility (GaAs), with a wide bandgap semiconductor (SnO2) which is naturally n-type, where Eu3+ emission is quite efficient. Samples of these two materials were initially investigated separately, as thin films, or SnO2:Eu powders pressed into pellets. Photoluminescence was measured in GaAs/SnO2:2%Eu heterostructures with thermal annealing at low temperature (200 and 400°C), while SnO2:2%Eu films showed Eu3+ emission peaks only when treated with higher temperature (1000°C), but with low intensity. The hypothesis for this phenomenon was associated with Eu3+ agglomerates on the sample surfaces. XAFS measurements have allowed the study of the incorporation of the Eu doping in the SnO2 matrix, and in the understanding of the mechanism of luminescence found. Analysis of XANES showed that the europium atom remains in the trivalent oxidation state after the synthesis of the solution and thermal annealing done, and that the GaAs/SnO2:2%Eu heterostructure presents less distortion in the lattice and more ordered structure when compared to films of SnO2:2%... (Complete abstract click electronic access below) / Doutor

In dieser Arbeit wird Femtosekunden-Spektroskopie im mittleren Infrarot angewandt auf einige der am gründlichsten studierten fotoinduzierten Reaktionen: der Wasserstoff-Protonentransfer im elektronischen angeregten Zustand, für einen intramolekularen und einen intermolekularen Fall, sowie die Isomerisation fotochromer Verbindungen. Elektronische Spektroskopie ist die am häufigsten verwendete Methode zur Untersuchung ultraschneller Reaktionsdynamik in der kondensierten Phase, wobei Übergänge zwischen elektronischen Zuständen der reagierenden molekularen Systeme beobachtet werden. Häufig werden elektronische Übergänge abgetastet, deren Wellenfunktionen delokalisiert sind, so dass kaum ortspezifische Information erhalten wird. Außerdem ist aufgrund der breiten Absorptionslinien, die aus den schnellen Dephasierungszeiten elektronischer Übergänge resultieren, eine verlässliche Interpretation der experimentellen Daten schwierig; dies umso mehr, je komplexer der Reaktion ist, z.B. durch die Anwesenheit verschiedener Isomere oder durch das Zusammenwirken vieler elektronischer Zustände. Femtosekunden-Infrarotspektroskopie wird in dieser Arbeit als leistungsfähige Alternative eingesetzt, um ultraschnelle Reaktionsdynamik zu beobachten, und so den hohen Grad an Korrelation zwischen Infrarotspektren und molekularer Struktur sowie die Vorteile schmaler Bandbreiten IR-aktiver Schwingungsmoden auszunutzen. / In this thesis femtosecond mid-infrared spectroscopy has been applied to the investigation of some of the most thoroughly studied photoinduced reactions: the excited state hydrogen/proton transfer, both in an intramolecular and in an intermolecular case, and the isomerization of photochromic compounds. Electronic spectroscopy is the most commonly used method for ultrafast studies of molecular reaction dynamics in the condensed phase, whereby the electronic states of the reacting molecular systems are monitored. These techniques typically probe electronic transitions occurring between delocalized orbitals and - thus - do not provide site-specific information. Besides, the broad absorption lines resulting from the fast dephasing times of electronic transitions in solutions may hinder a reliable interpretation of the experimental results, especially when the complexity of the reaction increases, due e.g. to the presence of different isomers or to the involvement of numerous electronic states. Femtosecond infrared spectroscopy has been used in this work as a powerful and complementary alternative to probe ultrafast reaction dynamics, exploiting the high degree of correlation between the infrared spectra and the molecular structure and the advantages stemming from the narrow bandwidths of IR-active vibrational modes.

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Dans ce travail, nous présentons la réalisation de composants originaux d’optique guidéeutilisant une technique de fabrication basée sur l'autofocalisation d’un faisceau lumineux.Cette technique permet la photo-induction de guides d’onde optiques au coeur de cristauxde LiNbO3 par effet photoréfractif.En premier lieu, des guides adiabatiques ont été générés dans des cristaux de LiNbO3 enappliquant un gradient de température selon l’axe de propagation lors de l’étaped’induction. Ces résultats expérimentaux ont été appuyés par un modèle numérique 3-Dprenant en compte la dynamique de l'effet photoréfractif.Dans un deuxième temps, nous avons démontré que la présence d’un micro-canal présentsur le trajet d’un faisceau ne perturbe pas son autofocalisation. Cette configuration a permisde fabriquer un capteur optofluidique qui permet de mesurer l'indice de réfraction d’unliquide présent dans le canal sur une plage de mesure de 1.2 à 1.8 avec une précision de4x10-3. Enfin, cette étude a été étendue à des faisceaux sous forts angles d’incidence avec lecanal ce qui a été exploité pour induire un séparateur de polarisation en optique guidée. Ceséparateur, fabriqué en une seule étape d’induction, est constitué d’un guide d’entrée seséparant en deux guides de sortie supportant des composantes croisées de polarisation. / In this work, we present the fabrication of innovative guided optics components using asimple and efficient method based on self-trapping of light beams. This technique leads tothe formation of optical waveguides inside LiNbO3 crystals by photorefractive effect.The generation of adiabatic waveguides is first achieved by applying a temperature gradientalong the propagation axis. These experimental results have been confirmed by a 3-Dnumerical model taking into account the photorefractive dynamic.Subsequently, we have shown that the presence of a micro-channel forming a gap on thebeam trajectory does not affect the self-trapping effect. This configuration has been used tofabricate an optofluidic sensor able to measure the refractive index of liquids present in thechannel with a measuring range between 1.2 and 1.8 and a resolution of 4x10-3. Finally, thisstudy has been extended to self-trapped beams at large angle of incidence with the channelwhich has been exploited to fabricate a guided polarization separator. This polarizationseparator is formed of one input waveguide that separates into two output waveguidessupporting crossed polarizations components.

En utilisant les spectroscopies d'absorption UV-vis et d'émission stationnaire et résolue dans le temps (femto- et sub–nanoseconde, caméra à balayage de fente), nous avons étudié, au cours de cette thèse, les processus photophysiques au sein de différentes molécules et supramolécules. Les propriétés photophysiques de nouveaux complexes de Ru(II) polypyridine et de Ir(III) cyclométallé présentant un transfert d'énergie électronique réversible entre le noyau métallique et les chromophores organiques auxiliaires énergétiquement appariés (anthracène et pyrène) ont été analysées en détail. Les caractéristiques de la séparation de charge entre un donneur d'électron (OPV) et un accepteur (PB) à travers un pont d'oligoquinoline au sein de foldamères de longueurs croissantes ont été précisées dans une échelle de temps inférieure à la nanoseconde. De nouvelles sondes luminescentes à base de lanthanides ont été réalisées pour la détection en temps réel de l’ion Cu(I), leurs propriétés optiques étant modulées par effet «d’antenne» par le biais d'interactions cations-nuagePi. L'étude de sondes fluorescentes off-on en proche IR formées de colorantsBF2-AzaBODIPY fixés de manière covalente sur des nanoparticules (100 nm) polymériques a été réalisée, et étendue à de nouvelles sondes sensibles au pH émettant dans le proche IR. Des études de photoisomérisation ont été effectuées sur deux systèmes azobenzéniques capables de libérer/capturer des ions Ca(II) (azobenzène-éther«lasso», azobenzène-BAPTA) – l'impact de l'eau sur la photoisomérisation cis-trans d’hydroxychalcones a été mis en évidence dans CH3CN et H2O/CH3OH (v/v=1/1). / In the present work photophysical processes of different molecular and supramolecular systems were studied using steady-state and time-resolved femto- and sub-nanosecond (streak-camera detection) UV-vis absorption and emission spectroscopies. Detailed photophysical studies of novel Ru(II) polypyridine and cyclometalatedIr(III) complexes showing reversible electronic energy transfer between metallic core and auxiliary organic energetically-matched chromophores anthracene and pyrene, respectively were performed. Time-resolved characterization of charge separation between electron donor (OPV) and acceptor (PB) in the sub-nanosecond timescale through an oligoquinoline bridge in foldamers of increasing oligomeric length was carried out. Novel lanthanide-based luminescent probes were investigated for time-gated detection of Cu(I) ion, being modulated by an antenna effect through cation-pi interactions.The study on NIR fluorescent off-on probes, based on BF2-aza-BODIPY dyes, covalently attached to the surface of polystyrene 100 nm nanoparticles, along with related novel NIR pH-responsive fluorescence probes were conducted. Photoisomerization studies focused on azobenzene-based (azobenzene-lariat ether, azobenzene-BAPTA)Ca(II)-ion release/capture systems, while the impact of water on the cis−trans photoisomerizationof hydroxychalcones was studied in CH3CN and H2O/CH3OH (v/v=1/1).

Availability of amorphous semiconductors in the form of high quality multilayers provide potential applications in the field of micro- and optoelectronics. Although the misfit problems in amorphous multilayers (AML) are considerably reduced compared to crystalline superlattices, there are still some physical processes (e.g. quantum confinement, diffusion) that are not well understood. Recently chalcogenide glass multilayers were prepared with high quality nanomodulation, which demonstrated their potential for tailoring the optical properties. Moreover studies on amorphous nanolayered chalcogenide structures (ANC) are still at the infant stage. These ANCs are similar to the crystalline superlattices, yet distinct from ideal crystalline superlattices produced by molecular beam epitaxy. The ANCs can be considered as well-correlated layers with good periodicity and smooth interface. They are attractive because of the prominent photoinduced effects, similar to those exhibited by uniform thin films. For example, photoinduced diffusion in short period multilayer systems is important because of its potential applications in holographic recording and fabrication of phase gratings. In spite of its practical usefulness, the mechanism of photoinduced interdiffusion is not properly understood. Since most structural changes are related to atomic diffusion, understanding of the structural transformation must be based on the diffusion process. Moreover, in AML, the process of interdiffusion is not well understood. The main aim of this thesis is to study the photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 nanolayered films. In literature, there are reports about the photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 nanolayered films, but the mechanisms of photoinduced interdiffusion of these elements are not properly understood. Raman scattering and infrared spectroscopy techniques were used to study the photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 nanolayered films by Kikineshi et al, but the results were not satisfactory. The characteristic spectra of components in the multilayer and those of the mixed layer were rather similar. In the present thesis, photoinduced interdiffusion in Se/As2S3 and Bi/As2S3 nanolayered samples are studied by optical absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Photoluminescence (PL). The detailed information about the distribution of electronic states in the absorption edge, localized states and the new bonds formed between the components due to photoinduced interdiffusion elucidated from the above studies will give more insight into the mechanism and kinetics of photoinduced interdiffusion. The thesis consists of six chapters. References are given at the end of each chapter. Various general and unique physical properties of amorphous chalcogenides are discussed in Chapter 1. This chapter summarizes the fundamental aspects of amorphous state, such as the structure and its models, electronic band structure, defects as well as the physical properties like d.c conductivity, a.c conductivity, optical absorption, photoconductivity and PL. A more detailed account of the various photoinduced effects are also discussed. Apart from this, similar photoinduced effects observed in other systems like a-Si:H, oxide glasses, Polymers etc are described in brief. Finally, the scope of present investigations is furnished. Chapter 2 has been devoted to photoinduced interdiffusion and related changes in optical properties of nanolayered Se/As2S3 films. It begins with a brief introduction followed by a survey of the earlier work done on these multilayered films. The theory of optical absorption and experimental procedures are discussed. Photoinduced interdiffusion was observed with above band gap light in nanolayered Se/As2S3 films. It is discussed in terms of the optical parameters such as bandgap, Urbach edge (Ee) and Tauc’s parameter (B1/2). From the analysis of the optical absorption spectra, it was concluded that the optical bandgap, Ee and B1/2 change with photoinduced interdiffusion. These changes in properties are ascribed to the solid solution formation due to the intermixing of adjacent layers. The photoinduced intermixing of the adjacent layers are obviously related to the photoinduced viscous flow and it depends on the number of excited chalcogen bridge atoms, which determine the local deformations due to the bond switching and displacements. Experimental data of B1/2 and Ee for as prepared samples do not show a clear correlation implied by the Mott-Davis model. It is also observed that the optical parameters can be changed with a change in the Se sublayer thickness. Variations of these optical parameters as a function of modulation period and photoinduced interdiffusion were discussed in terms of the quantum confinement effect and changes in the valence and conduction bands. Chapter 3 deals with the PL studies on as prepared and irradiated samples of Se/As2S3 nanolayered films. The theory of PL, experimental procedures and data analysis are discussed in detail. PL studies were carried out on as prepared and irradiated nanolayered samples of Se/As2S3 films. None of the samples showed PL at 77 K, which clearly indicate that there exists a competitive non-radiative mechanism. We observed a broad PL in the range of 0.8–1.2 eV for as prepared and irradiated samples at 4.2 K. The observed stoke shift in PL is discussed in terms of the strong electron-phonon coupling at the recombination centers. We found that the PL intensity can be increased by several orders of magnitude by irradiating the samples with appropriate wavelengths in the range of the absorption edge. The broadening of luminescence bands takes place either with a decrease in Se layer thickness or with irradiation. The former is due to the change in interface roughness while the latter is due to photoinduced interdiffusion. Deconvolution showed that the PL spectrum consists of five transitions. The deconvoluted peak PL intensity, PL quantum efficiency and full width at half maximum are varying according to the function of sublayer thickness and interdiffusion. All these results indicate the high impact of interdiffusion on the luminescence intensity in the given AML is due to changes of defect states, which in turn are not directly connected to the band structure, i.e., confinement effects are not essential for this type of luminescence. The whole picture is complex due to more complicated carrier relaxation and recombination process, possibly with several interconnected effects, which are not properly understood, but the possibility for tuning the optical parameters of the Se/As2S3 nanolayered films, including the low temperature luminescence, is established. Chapter 4 is on kinetics and chemical analysis of photoinduced interdiffusion in nanolayered Se/As2S3 films. The basic formalism of X-ray photoelectron spectroscopy and in situ optical absorption spectroscopy together with a brief description of the theory and data analysis adopted in the present studies are given. We have studied the kinetics of photoinduced interdiffusion in nanolayered Se/As2S3 film by in situ optical absorption measurements. All previous measurements were performed ex situ, i.e., a film exposed under light irradiation during the measurement was never studied. In situ changes in the transmission spectra were measured, but at a fixed wavelength. Since the measurements were done on a single wavelength, the kinetics of the variation of optical bandgap and Tauc parameter were missing. In short, information has been missing about the metastable changes in the multilayer structure during photoinduced interdiffusion. In situ changes in transmission spectra were recorded over the wavelength range λ=400-1000 nm, and also at fixed wavelengths to understand the changes in absorption coefficient, optical bandgap and Tauc parameter during photoinduced interdiffusion. The in situ optical absorption measurements reveal that the photo darkening in amorphous nanolayered Se/As2S3 film is followed by photoinduced interdiffusion. An increase in disorder during photodarkening and its subsequent decrease during photoinduced interdiffusion was also observed. The observation of photodarkening of Se at room temperature when confined between As2S3 layers suggests that the glass transition temperature of Se shifts to higher temperature. The analysis shows that the atoms, which take part in photodarkening, play a vital role in photoinduced interdiffusion. We used XPS to analyze the new bonds formed between the components due to photoinduced interdiffusion. The XPS results showed that there is a considerable decrease in the As-S, As-As and S-S bonds after photoinduced interdiffusion; As-O and some of the S-S homopolar bonds are retained. There was a considerable decrease in As-S bond followed by an increase in As-Se and S-Se bonds. XPS analysis also shows that during photodiffusion, heteropolar bonds replace homopolar bonds, i.e., the irradiated samples are chemically ordered than the corresponding as prepared samples. Chapter 5 is concerned with the photoinduced interdiffusion in Bi/As2S3 nanolayered films. A brief description about the photoinduced interdiffusion of metals such as Ag, Zn, etc is given in the introduction. The experimental procedures and data analysis are also given. Two sets of samples with different ratios of sublayer thickness (d), d-Bi/d-As2S3 = 1/12 and 1/6 prepared by cyclic thermal evaporation are employed for the present study. A pump probe optical absorption technique was used to study the photoinduced interdiffusion in Bi/As2S3 nanolayered samples. Photoinduced interdiffusion of Bi into As2S3 was observed in both the films. The XPS analysis shows that the as prepared samples contain a large number of wrong As–As bonds and some of the As-As bonds are converted to As-S bonds during irradiation. The XPS analysis also reveals that the Bi is forming only bond with S during photoinduced interdiffusion. Chapter 6 summarizes the essential features of the present work and also points a few possible directions along which further work can be carried out.

Τα τελευταία έτη η σύνθεση και ο χαρακτηρισμός μονοδιάστατων νανοδομών αποκτά αυξανόμενο ερευνητικό ενδιαφέρον καθώς συνδυάζουν φαινόμενα από την νάνο κλίμακα με την δυνατότητα χειρισμού τους λόγω του μεγάλου μήκους τους. Εκτός από τα καθιερωμένα υλικά με αυτήν την μορφολογία όπως είναι οι νανοσωλήνες άνθρακα, οι νανοράβδοι οξειδίου του ψευδαργύρου και τα νανοκαλώδια πυριτίου μία κατηγορία υλικών που αναπτύσσει τέτοιες νανοδομές είναι τα χαλκογενή Σελήνιο και Τελλούριο γεγονός που εξηγείται από την υψηλής ανισοτροπίας κρυσταλλική τους δομή. Στόχος αυτής της εργασίας είναι η παραγωγή, μέσω φωτοαποδόμησης, νανοσωλήνων Τελλουρίου οι οποίοι μέσω φωτοοξείδωσης μετατρέπονται σε νανοκαλώδια Οξειδίου του Τελλουρίου. Η διερεύνηση της κινητικής του φαινομένου ανάλογα με το χρησιμοποιούμενο μήκος κύματος και την ένταση της ακτινοβολίας καθώς και ο χαρακτηρισμός των παραγόμενων νανοδομών γίνεται με φασματοσκοπία Raman. Τα συμπεράσματα στα οποία καταλήγουμε ενισχύονται από μία σειρά άλλων πειραματικών μεθόδων όπως περίθλαση ακτίνων Χ (XRD) και ηλεκτρονική μικροσκοπία σάρωσης και διέλευσης (SEM, TEM). / One dimensional (1D) nanostructures of semiconducting oxides and elemental chalcogens culminate over the last decade in nanotechnology owing to their unique properties exploitable in several applications sectors. Whereas several synthetic strategies have been established for rational design of 1D materials using solution chemistry and high temperature evaporation methods, much less attention has been given to the laser-assisted growth of hybrid nanostructures. Here, we present a laser-assisted method for the controlled fabrication of Te nanotubes. A series of light-driven phase transition is employed to controllably transform Te nanotubes to core-Te/sheath-TeO2 and/or even neat TeO2 nanowires. This solid-state laser-processing of semiconducting materials apart from offering new opportunities for the fast and spatially controlled fabrication of anisotropic nanostructures, provides a means of simultaneous growing and integrating these nanostructures into an optoelectronic or photonic device.

Photoinduced electron transfer is involved in a number of photochemical and photobiological processes. One example of this is photosynthesis, where the absorption of sunlight leads to the formation of charge-separated states by electron transfer. The redox equivalents built up by successive photoabsorption and electron transfer is further used for the oxidation of water and reduction of carbon dioxide to sugars. The work presented in this thesis is part of an interdisciplinary effort aiming at a functional mimic of photosynthesis. The goal of this project is to utilize sunlight to produce renewable fuels from sun and water. Specifically, this thesis concerns photoinduced electron transfer in donor(D)-photosensitizer(P)-acceptor(A) systems, in mimic of the primary events of photosynthesis. The absorption of a photon typically leads to transfer of a single electron, i.e., charge separation to produce a single electron-hole pair. This fundamental process was studied in several molecular systems. The purpose of these studies was optimization of single electron transfer as to obtain charge separation in high yields, with minimum losses to competing photoreactions such as energy transfer.Also, the lifetime of the charge separated state and the confinement of the electron and hole in three-dimensional space are important in practical applications. This led us to explore molecular motifs for linear arrays based on Ru(II)bis-tridentate and Ru(II)tris-bidentate complexes. The target multi-electron catalytic reactions of water-splitting and fuel production require a build-up of redox equivalents upon successive photoexcitation and electron transfer events. The possibilities and challenges associated with such processes in molecular systems were investigated. One of the studied systems was shown to accumulate two electrons and two holes upon two successive excitations, without sacrificial redox agents and with minimum yield losses. From these studies, we have gained better understanding of the obstacles associated with step-wise photoaccumulation of charge and how to overcome them.

Photodynamic therapy (PDT) is an alternative treatment of cancer requiring the use of chromophore molecules (photosensitizers), which can induce cell death after light excitation. Gold nanoparticles (AuNP), exhibiting localized Surface Plasmon Resonance, can enhance the photophysical response of chromophores located in their vicinity, and thus improve their therapeutic action. Moreover, the use of highly localized two-photon chromophores (photosensitizers and fluorophores), capable to undergo a localized excitation by light in the Near InfraRed region, should increase the penetration depth into tissues, thus improve the treatment efficiency (by PDT) and the imaging (by fluorescence microscopy) of cancer tissues.In this work, we describe the elaboration of water-soluble hybrid nano-objects for PDT and fluorescence bioimaging applications, composed of two-photon chromophore-polymer conjugates grafted onto gold nanoparticles. In order to obtain these nano-objects we follow a multistep strategy: i) the synthesis of a well-defined water-soluble chromophore-polymer conjugates; ii) the end-group oriented grafting of chromophore-polymer conjugates onto 20 nm AuNP. The coupling of hydrophobic two-photon chromophores on linear water-soluble copolymer chains (poly(N-acryloylmorpholine-co-N-acryloxysuccinimide)), obtained by controlled/living RAFT polymerization, resulted in well-defined water-soluble chromophore-polymer conjugates, with different polymer lengths (2 000 g.mol-1 < Mn < 37 000 g.mol-1) and architectures (random or block), and a controlled number of chromophores per chain (varying between 1 and 21). Their grafting onto 20 nm AuNP gave water-soluble hybrid nano-objects with high grafting densities (~0.5 chains/nm²). The role of the polymer chain being to tune the distance between chromophores and AuNP surface, we have evidenced the increase in the polymer corona thickness of grafted AuNP (estimated by TEM) with the increasing polymer Mn, corroborating with the corresponding distance-dependent fluorescence properties of those. Finally, the in cellulo biological properties of two-photon chromophore-polymer conjugates, before and after grafting onto AuNP, have been investigated, highlighting their potential for two-photon bioimaging and PDT applications.

Copper is an essential trace element for living organisms and has both known and additional suspected roles in human health and disease. The current understanding of copper metabolism is substantial but incomplete, particularly in regard to storage and exchange at the subcellular level, although available evidence indicates exchangeable intracellular copper is in the monovalent oxidation state. Selective fluorescent probes with sufficient sensitivity to detect Cu(I) availability at physiologically relevant levels and at subcellular resolution would be valuable tools for studying copper metabolism. As a contribution toward this goal, this work describes the development of Cu(I)-selective fluorescent probes with greatly improved aqueous solubility, contrast ratio, and fluorescence quantum yield. This work also describes the development of water-soluble, 1:1-binding chelators that form colorless, air-stable copper(I)-complexes. By acting as copper(I) buffering agents and affinity standards, these compounds can serve a complementary role to fluorescent probes in the study of copper biochemistry.