Oxidation of Copper(I) in seawater at nanomolar levels

The oxidation and reduction of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17-8.49), temperature (5-35ºC) and ionic strength (0.1-0.7 M). The oxidation rate was fitted to an equation for sodium chloride and seawater valid at different pH and media conditions: k . . pH- . /T- . I . I k . . pH- . /T- . I . I (sw) (NaCl) log 5 036 0 514 1764 915 1101 0 233 log 5 221 0 609 1915 433 1818 0 408 = + + = + + The reduction of Cu(II) was studied in both media for different initial concentration of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) produced was 20% and 9% for NaCl and seawater, respectively. Considering the copper(I) reduced from Cu(II), the speciation and the contribution of these species to the kinetic process was studied. The Cu(I) speciation is dominated by the CuCl2 - species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range 0.1 M to 0.7 M chloride concentrations.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

Edaravone containing isoindoline nitroxides for the potential treatment of cardiovascular ischaemia

A novel antioxidant for the potential treatment of ischaemia was designed by incorporating an isoindoline nitroxide into the framework of the free radical scavenger edaravone. 5-(3-Methyl-pyrazol-5-ol-1-yl)-1,1,3,3-tetramethylisoindolin-2-yloxyl 7 was prepared by N-arylation of 3-methyl-5-pyrazolone with 5-iodo-1,1,3,3-tetramethylisoindoline-2-yloxyl 8 in the presence of catalytic copper(I)iodide. Evaluation of 7, its methoxyamine derivative 10 and 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (CTMIO) against edaravone 1 in ischaemic rat atrial cardiomyocytes revealed significant decreases in cell death after prolonged ischaemia for each agent; however the protective effect of the novel antioxidant 7 (showing greater than 85% reduction in cell death at 100 μM) was significantly enhanced over that of edaravone 1 alone. Furthermore, the activity for 7 was found to be equal to or greater than the potent cardioprotective agent N6-cyclopentyladenosine (CPA). The methoxyamine adduct 10 and edaravone 1 showed no difference between the extent of reduction in cell death whilst CTMIO had only a modest protective effect.

Synthesis and characterisation of new platinum-acetylide complexes containing diimine ligands

A new class of platinum-bipyridyl compounds has been synthesized by the dehydrohalogenative reaction of [4,4'-bis(tert-butyl)-2,2'-bipyridyl]platinum dichloride [PtCl2((t)Bu(2)bipy)] 1 with terminal alkynes HC=CR, in the presence of copper(I) iodide and diisopropylamine. The products [Pt(C=CR)(2)((t)Bu(2)bipy)] (R=C6H4NO2-p 2, C6H5 3, C6H4CH3-p 4 or SiMe3 5), have been characterised by spectroscopic and analytical methods, and a single crystal molecular structure determination has been carried out on 4. Extended Huckel molecular orbital calculations have also been carried out, and the results are used to help rationalise the voltammetric, EPR and spectroelectrochemical properties of the new compounds. These show that compounds 3, 4 and 5 undergo a one-electron bipyridyl based redox process, but that 2 has an unresolved two-electron process located on the nitro groups.

An operationally simple sonogashira reaction for an undergraduate organic chemistry laboratory class

An operationally simple, reliable, and cheap Sonogashira reaction suitable for an undergraduate laboratory class that can be completed within a day-long (8 h) laboratory session has been developed. Cross-coupling is carried out between 2-methyl-3-butyn-2-ol and various aryl iodides using catalytic amounts of bis-(triphenylphosphine)palladium(II) dichloride, with copper(I) iodide as a cocatalyst, in triethylamine at room temperature, so a range of products can be prepared within a single group and results compared. The coupling itself is usually complete within 1.5 h and is easily monitored by TLC, leaving up to 6 h for purification and characterization. Purification is by “mini flash column chromatography” through a plug of silica encased in the barrel of a plastic syringe, so the procedure is amenable to large class sizes.

Novel cross-coupling reactions between organotellurides and Grignard reagents employing a MnCl2/CuI catalytic system

We present a general protocol for the cross-coupling reaction of Grignard reagents and organic tellurides. Aryl Grignard reagents react stereospecifically with vinyl tellurides in the presence of a catalytic amount of manganese (II) chloride and copper (I) iodide to produce good yields of the corresponding cross-coupling products. (C) 2012 Published by Elsevier Ltd.

Synthese und Struktur-Eigenschafts-Beziehungen von Oligo- und Poly(2,5-dipropoxy-1,4-phenylenethinylen)en

Oligomere mit konjugierten pi-Elektronensystemen sind für die Materialwissenschaften von großer Bedeutung. Die vielfältigen und umfangreichen Forschungen auf diesem Gebiet gründen im Potenzial dieser Substanzklassen, das im Bereich der Laserfarbstoffe, Leuchtdioden, Photoleiter, optische Schalter oder auch der molekularen Elektronik angesiedelt ist. Zu diesen gehören auch die in dieser Arbeit synthetisierten und untersuchten Phenylenethinylene. Die Herstellung der Oligomere erfolgt nach der Methode von Sonogashira und Hagihara. Dabei wird ein Halogenaren mit einer Alkinkomponente zur Reaktion gebracht. Als Katalysator dient dabei ein Gemisch aus Bis(triphenylphosphin-palladiumdichlorid), Kupfer-(I)-iodid und Triphenylphosphin. Verwendung fanden bei der Synthese zwei Arten von Schutzgruppen. Es handelt sich dabei einerseits um die Trimethylsilyl- und die Triisopropylsilyl-Funktion, die unabhängig voneinander in ein System eingeführt werden und selektiv wieder entfernt werden können. Die zweite Art sind die Halogene Brom und Iod, die aufgrund ihrer Eigenschaft vielmehr als 'dormant group' bezeichnet werden müssen. Eine Ethinylierung führt zunächst zur Substitution des Iod- und anschließend des Bromatoms. Die so erhaltenen Oligomere werden mit verschiedenen spektroskopischen Methoden untersucht. Besonderes Interesse liegt dabei auf der Bestimmung der effektiven Konjugationslänge (EKL). Damit ist es möglich, die Länge des konjugierten Systems zu bestimmen, das für die betreffenden Eigenschaften des entsprechenden Polymers maßgeblich ist. Das nichtlineare optische Verhalten der Oligomere wird mittels der Third-Harmonic-Generation-Methode (THG) gemessen. Die resultierende Größe, die Suszeptibilität 3. Ordnung, gibt Aufschluß über mögliche industrielle Anwendungen.

Reaktionen monovalenter Münzmetalle in flüssigem Ammoniak

Im Rahmen dieser Arbeit konnten erstmals eine Reihe von Ammoniakaten von Münzmetallhalogeniden (M(I)Hal) und Pseudohalogeniden aus flüssigem Ammoniak in einkristalliner Form isoliert und strukturell charakterisiert werden. Mit dem Ammoniakat des Gold(I)-iodids wurden Metathesen in flüssigem Ammoniak durchgeführt, die die Isolierung einiger sehr thermolabiler, teilweise explosiver Alkoholate des Golds ermöglichten. Die Bestimmung der Kristallstruktur eines Gold(I)-phenolates erlaubte erste Einblicke in deren Aufbau.rnIn der Reihe der Ammoniakate der M(I)Hal mit Ausnahme von Silberiodid, werden keine direkten Metall-Halogen-Kontakte ausgebildet. Die Ammoniakate der Chloride und Bromide des Kupfers und Silbers sowie des Kupferiodids besitzen isotype Strukturen. Sie liegen als Trisammoniakate [M(NH3)3]Hal vor. Im Ammoniakat von Silberiodid besitzen die Silberionen durchgängig die Koordinationszahl 4. Neben Ag•••NH3- findet man auch direkte Kationen-rnAnionen-Kontakte und sehr kurze Ag(I)-Ag(I)-Abstände. Das Goldkation im Ammoniakat von Goldiodid besitzt die Koordinationszahl 2 und wird ausschließlich durch Ammoniakmoleküle koordiniert. Die gebildeten H3N-NH3-Hanteln werden über aurophile Wechselwirkungen verknüpft.rn rnDie Ammoniakate der Cyanide von Silber und Gold, enthalten molekulare Baueinheiten des Typs:(H3N)nMCN [(n= 1 für M= Au und n= 2 für M= Ag].rnrnAnders als bei den solvatfreien Homologen wird eine Ausbildung von Polymerketten nicht beobachtet. Das linear aufgebaute Ammoniakat von Goldcyanid ermöglicht die Ausbildung von aurophilen Wechselwirkungen. Metallophile Wechselwirkungen zwischen dem als Dimer vorliegenden Ammoniakat von AgCN scheinen nicht ausgebildet zu werden.rnrnMetatheseversuche von Goldiodid mit einem Amid und diversen Alkanolaten lieferten teilweise explosive Produkte. Es ist davon auszugehen, dass mit zunehmender Basizität der eingesetzten Anionen, die an das Gold(I)-ion koordinierten Ammoniakmoleküle deprotoniert werden und explosives Goldamid gebildet wird. Der als zweites Produkt entstehende Alkohol kann ebenfalls ein Ammoniakat bilden. Im Fall von Li-Fencholat wird ein solches in Form sehr tiefschmelzender Einkristalle erhalten.rnrnDa die Deprotonierung der an Gold koordinierten Ammoniakmoleküle unweigerlich zu explosiven oder sehr instabilen Produkten führt, wurde die geringere Basizität der Phenolate ausgenutzt, um dies zu umgehen. Im Falle der Umsetzung von AuI mit Li-2,6-di-tert.-butylphenolat gelang tatsächlich die Isolierung eines kristallinen Gold(I)-phenolats.rn

Crystal Engineering of bright luminescent copper iodide clusters with phosphorus and nitrogen-based ligands

Copper(I) halide clusters are recently considered as good candidate for optoelectronic devices such as OLEDs . Although the copper halide clusters, in particular copper iodide, are very well known since the beginning of the 20th century, only in the late ‘70s the interest on these compounds grew dramatically due their particular photophysical behaviour. These complexes are characterized by a dual triplet emission bands, named Cluster Centred (3CC) and Halogen-to-Ligand charge transfer (3XLCT), the intensities of which are strictly related with the temperature. The CC transition, due to the presence of a metallophylic interactions, is prevalent at ambient temperature while the XLCT transition, located preferentially on the ligand part, became more prominent at low temperature. Since these pioneering works, it was easy to understand the photophysical properties of this compounds became more interesting in solid-state respect to solution with an improvement in emission efficiency. In this work we aim to characterize in SS organocopper(I)iodide compounds to valuate the correlation between the molecular crystal structure and the photophysical properties. It is also considered to hike new strategies to synthesize CuI complexes from the wet reactions to the more green solvent free methods. The advantages in using these strategies are evident but, obtain a single crystal suitable for SCXRD analysis from these batches is quite impossible. The structure solution still remains the key point in this research so we tackle this problem solving the structure by X-ray powder diffraction data. When the sample was fully characterized we moved to design and development of the associated OLED-device. Since copper iodide complexes are often insoluble in organic solvents, the high vacuum deposition technique is preferred. A new non-conventional deposition process have also been proposed to avoid the low complex stability in this practice with an in-situ complex formation in a layer-by layer deposition route.

Structural model for the Cu-B site of dopamine beta-hydroxylase: Crystal structure of a copper(II) complex showing N3OS coordination with an axial sulfur ligation

A copper(II) complex containing a NSO-donor Schiff base and NN-donor 2,2'-bipyridine has been prepared and structurally characterized. The square pyramidal complex with an axial sulfur ligation is a structural model for the CUB site of dopamine-hydroxylase in its oxidized form. The copper(II) complex is catalytically active in the oxidation of ascorbic acid by dioxygen mediated by a copper(I) species which is proposed to have a four-coordinate structure with a N3S coordination geometry.

Synthesis and structure of La14V6CuO36.5: a transparent Cu(I) vanadate containing [OCuO](3-) sticks

The title compound, La14V6CuO36.5, was prepared from a stoichiometric mixture of La2O3,V2O5, and CuO at 1050-1080 degreesC. The compound forms transparent, pale green crystals and was characterized by wavelength dispersive spectroscopy and single crystal X-ray diffraction. The structure contains isolated VO43- tetrahedra and [OCuO](3-) sticks dispersed in a lanthanum oxide network. Films of La14V6CuO36.5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, a similar to5 eV optical band gap and n-type conductivity. The compound is an example of a transparent copper(I) oxide.

Remarkable photocytotoxicity in hypoxic HeLa cells by a dipyridophenazine copper(II) Schiff base thiolate

Copper(II) complexes Cu(satp)(L)] (1-3) of a Schiff base thiolate (salicylidene-2-aminothiophenol, H(2)satP) and phenanthroline bases (L), viz. 1,10-phenanthroline (phen in 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 3), were prepared, characterized and their anaerobic DNA photocleavage activity and hypoxic photocytotoxicity studied. The redox active complexes show the Cu(II)-Cu(I) couple near -0.5 V for 1 and near 0.0 V vs. SCE (saturated calomel electrode) for 2 and 3. The one-electron paramagnetic complexes (similar to 1.85 mu(B)) are avid DNA binders giving K(b) values within 1.0 x 10(5) - 8.0 x 10(5) M(-1). Thermal melting and viscosity data along with molecular docking calculations suggest DNA groove and/or partial intercalative binding of the complexes. The complexes show anaerobic DNA cleavage activity in red light under argon via type-I pathway, while DNA photocleavage in air proceeds via hydroxyl radical pathway. The DFT (density functional theory) calculations reveal a thyil radical pathway for the anaerobic DNA photocleavage activity and suggest the possibility of generation of a transient copper(I) species due to bond breakage between the copper and sulfur to generate the thyil radical. An oxidation of the copper(I) species is likely by oxygen in an aerobic medium or by the buffer medium in an anaerobic condition. Complex 3 exhibits significant photocytotoxicity in HeLa cells (IC(50) = 8.3(+/- 1.0) mu M) in visible light, while showing lower dark toxicity (IC(50) = 17.2(+/- 1.0) mu M). A significant reduction in the dark toxicity is observed under hypoxic cellular conditions (IC(50) = 30.0(+/- 1.0) mu M in dark), while retaining its photocytotoxicity (IC(50) = 8.0(+/- 1.0) mu M). (C) 2011 Elsevier Inc. All rights reserved.