Correction: Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes.

[This corrects the article DOI: 10.1039/D2RA05341A.].

Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes.

A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for K D (4.0 to 70.0 M-1 range), ΔH (-1.4 to -2.6 kcal mol-1 range), ΔS (-0.2 to 2.1 cal mol-1 K-1 range), and ΔG 298 (-0.8 to -2.0 kcal mol-1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria.

Enhanced Charge Carrier Separation in WO3/BiVO4 Photoanodes Achieved via Light Absorption in the BiVO4 Layer.

Photoelectrochemical (PEC) water splitting converts solar light and water into oxygen and energy-rich hydrogen. WO3/BiVO4 heterojunction photoanodes perform much better than the separate oxide components, though internal charge recombination undermines their PEC performance when both oxides absorb light. Here we exploit the BiVO4 layer to sensitize WO3 to visible light and shield it from direct photoexcitation to overcome this efficiency loss. PEC experiments and ultrafast transient absorption spectroscopy performed by frontside (through BiVO4) or backside (through WO3) irradiating photoanodes with different BiVO4 layer thickness demonstrate that irradiation through BiVO4 is beneficial for charge separation. Optimized electrodes irradiated through BiVO4 show 40% higher photocurrent density compared to backside irradiation.

Spectroscopic Study of the E/Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer†.

The new cyrhetrenyl acylhydrazone [(CO)3 Re(η5 -C5 H4 )-C(O)-NH-N = C(CH3 )-(2-C4 H2 S-5-NO2 )] (E-CyAH) has been designed, synthesized and fully characterized to study the effect of having a cyrhetrenyl fragment (sensitizer) covalently bonded to an acylhydrazone moiety (switch), on its photophysical and photochemical properties. The crystal structure reveals that E-CyAH adopts an E-configuration around the iminic moiety [-N = C(CH3 )]. The absorption spectrum of E-CyAH displays two bands at 270 and 380 nm, which are mainly ascribed to π â†’ π* intraligand (IL) and dπ  â†’ π* metal-to-ligand charge transfer (MLCT) transitions, being consistent with DFT/TD-DFT calculations. Upon 365 nm irradiation, E-CyAH photoisomerizes to Z-CyAH, as evidenced by UV-Vis and 1 H-NMR spectral changes, with a quantum yield value ΦE -CyAH → Z -CyAH of 0.30. Z-CyAH undergoes a first-order thermal back-isomerization process, with a relatively short half-life τ1/2 of 277 min. Consequently, E-CyAH was quantitatively recovered after 24 h, making it a fully reversible T-type molecular photoswitch. This remarkable behavior allows us to measure the individual photophysical properties for both isomers. In addition, E-CyAH and Z-CyAH efficiently photosensitize the generation of singlet oxygen (O2 (1 Δg )) with good yield (ΦΔ  = 0.342).

Structural diversity in Cu(i) complexes of the PNP ligand: from pincer to binuclear coordination modes and their effects upon the electrochemical and photophysical properties.

A set of new copper(i) complexes is synthesized and characterized using a labile PNP pincer ligand (PNP = N,N'-bis(diphenylphosphine)-2,6-diaminopyridine). A homoleptic Cu(i) complex [Cu(PNP-κP1:κN1)2]+, (1), was prepared, and taking advantage of the uncoordinated phosphorus atoms in (1), reaction with a second Cu(i) atom bearing secondary ligands (PPh3, phen or dmp) allows the formation of new complexes: a bimetallic helicate [Cu(PNP)2(phen)]2+, (2), a mononuclear pincer complex [CuI(PNP)(PPh3)]+, (3), and a heteroleptic complex [CuI(PNP)(dmp)]+, (4). All complexes were characterized by X-ray crystallography, NMR (VT-NMR for (1) and (4)), cyclic-voltammetry, and steady-state and time-resolved luminescence spectroscopy. The fluxional behavior in (1) was studied by 31P VT-NMR, where an Ea value of 47.42 kJ mol-1 was calculated for the intramolecular alternating coordination of -PPh2 moieties in PNP to the metal atom. This set of compounds reveals the versatility of the PNP ligand when added to the coordinating properties of Cu(i). The four complexes exhibit emission in solution and complexes (2)-(4) display intense luminescence in the solid state. The oscillographic traces showing the decay of the luminescence were fitted to biexponential functions with time constants: 8.0 µs > τem,1 > 0.37 µs and 50 µs >τem, 2 > 2.2 µs for complexes (2), (3) and (4), respectively. Radiative relaxation is associated with electronic transitions in both the ligand PNP and metal-to-ligand charge transfer (MLCT).

AgInS2-ZnS Quantum Dots: Excited State Interactions with TiO2 and Photovoltaic Performance.

Multinary quantum dots such as AgInS2 and alloyed AgInS2-ZnS are an emerging class of semiconductor materials for applications in photovoltaic and display devices. The nanocrystals of (AgInS2)x-(ZnS)1-x (for x = 0.67) exhibit a broad emission with a maximum at 623 nm and interact strongly with TiO2 nanostructures by injecting electrons from the excited state. The electron transfer rate constant as determined from transient absorption spectroscopy was 1.8 × 1010 s-1. The photovoltaic performance was evaluated over a period of a few weeks to demonstrate the stability of AgInS2-ZnS when utilized as sensitizers in solar cells. We report a power conversion efficiency of 2.25% of our champion cell 1 month after its fabrication. The limitations of AgInS2-ZnS nanocrystals in achieving greater solar cell efficiency are discussed.

Two Distinct Transitions in Cu(x)InS2 Quantum Dots. Bandgap versus Sub-Bandgap Excitations in Copper-Deficient Structures.

Cu-deficient CuInS2 quantum dots (QDs) synthesized by varying the [Cu]:[In] ratio allow modulation of optical properties as well as identification of the radiative emission pathways. Absorption and emission spectral features showed a strong dependence on the [Cu]:[In] ratio of CuxInS2 QDs, indicating two independent optical transitions. These effects are pronounced in transient absorption spectra. The bleaching of band edge absorption and broad tail absorption bands in the subpicosecond-nanosecond time scale provide further evidence for the dual optical transitions. The recombination process as monitored by photoemission decay indicated the involvement of surface traps in addition to the bandgap and sub-bandgap transitions. Better understanding of the origin of the optical transitions and their influence on the photodynamics will enable utilization of ternary semiconductor quantum dots in display and photovoltaic devices.

Resolution and characterization of helicate dimer and trimer complexes of 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane with copper(I).

Complexation of copper(I) with the binucleating ligand, 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane, mphenpr, result in formation of helical dimers, [Cu2(mphenpr)2](2+). The resolution of the enantiomeric forms of the dimers has been carried out with Δ-[As(cat)3](-) as resolving agent and X-ray structures for two compounds, P-[Cu2(mphenpr)2](Δ-[As(cat)3])2 and P-[Cu2(mphenpr)2](Δ-[As(cat)3])2·4(CH3CN), are reported. The rate of racemization in poorly-coordinating solvents has been examined by (1)H NMR, and is slow. At saturating concentrations of [[Cu2(mphenpr)2](2+)] in acetonitrile, crystals of the helical trimeric complex [Cu3(mphenpr)3](ClO4)3 are obtained. The X-ray structure of the trimer is reported. This species has also been resolved. As with the helical dimer, racemization in poorly-coordinating solvents is slow, and circular dichroism and (1)H NMR spectra are reported. The absolute configuration of the resolved complex, P-[Cu3(mphenpr)3](Δ-[As(cat)3])3, has been determined by X-ray crystallography.

Nefrostomía percutánea ecoguiada con catéter Arrow: experiencia en el servicio de urología del Hospital Carlos Van Buren de Valparaíso entre los años 2008-2011 / Ecographic guiden percutaneus nephrostomy with Arrow catheter: experience in the urology service of the Carlos Van Buren of Valparaiso between 2008-2011

La nefrostomía es una técnica urológica que permite la derivación temporal de la vía urinaria buscando con esto preservar la función renal, aliviar el dolor y/o drenar la orina infectada. En el servicio de urología del Hospital Van Buren se implementó una técnica de nefrostomía percutánea ecoguiada con catéter Arrow 14 que ha permitido tratar precozmente a pacientes con patología urinaria obstructiva, con complicaciones menores y bajo costo...

Nephrostomy is an urologic technique that allows the temporary derivation of the urinary tract allowing with this to preserve the renal function, to alleviate the pain, to drain tinkles it infected. ln the Service of Urology of the Hospital Van Buren a percutaneous technique of nefrostomy has been ¡implemented guided by echography that has allowed treats to tens about patients with obstructive urinary pathology in precocious form, with smaller complications and low cost...

Micción obstructiva posterior a cinta suburetral: manejo sin uretrólisis regulando la malla de acuerdo a presión de escape intraoperatorio / Obstructive micturiction posterior to suburethral sling: management of urethrolysis according to intraoperative leak pressure

Introducción: La micción obstructiva es complicación frecuente posterior a la cirugía para incontinencia de orina con cinta suburetral. El tratamiento convencional de la presentación tardía es la uretrólisis por vía abdominal o vaginal. Ésta técnica corresponde a una cirugía invasiva, que puede requerir varios procedimientos y a nuestro parecer, no se relaciona con la patogenia de la disfunción miccional postoperatoria. Objetivos: Describir el manejo quirúrgico de pacientes con micción obstructiva posterior a cinta suburetral, sin uretrólisis, con sección de la cinta y disminuyendo la presión de escape intraoperatoria (PE-IO). Además mostrar los resultados obtenidos con su aplicación en el Hospital Carlos Van Buren. Material y métodos: De 1.240 cirugías con cinta suburetral, se consideraron obstructivas las pacientes que presentaron síntomas irritativos más uruflujometría patológica con residuo posmiccional (RPM) elevado o estudio flujo/presión obstructivo. Con anestesia espinal se seccionó la malla suburetral y se descendió la uretra hasta alcanzar un escape con Valsalva de 35 cm de agua. Se evalúan datos como mejoría sintomática, uroflujometría, RPM y estudio flujo/presión. Resultados: Se describen los resultados de 12 pacientes: 7 TVT y 5 TOT. Todas consultaron por síntomas de disfunción miccional y en el 100 por ciento se objetivó uropatía obstructiva previo a la segunda cirugía. Con anestesia espinal y vejiga llena con 300 cc, 4 presentaron escape sobre 60 cm de agua y 8 sobre 80 cm de agua. Una vez seccionada la malla se ajusta para PE-IO de 35 cm de agua. Se obtuvo mejoría clínica y urodinámica en el 100 por ciento de los casos que completaron seguimiento (11/12). Conclusiones: Las pacientes obstructivas posterior a cinta suburetral, presentan presión de escape intraoperatorio elevado (bajo anestesia espinal). La regulación de tensión de la cinta suburetral para obtener escape con Valsalva a 35 cm de agua, permite...

Introduction: Obstructive micturition (OM) is a frequent complication after suburethral sling (SL) placement for urinary incontinence. Abdominal or vaginal urethrolysis is the preferred treatment, however this invasive technique may require several attempts and it is our belief that this does not relate to postoperative urinary dysfunction. Objective: To describe surgical management of patients with OM secondary to SL without urethrolysis, by performing a sling section and decreasing intraoperative leak pressure (IOLP) at our institution. Material and methods: Of 1240 patients with SL, OM was considered to be present if voiding symptoms along with obstructive flowmetry and elevated urinary residue was found. SL is sectioned under spinal anaesthesia and the urethra is descended until a 35 cm water valsalva leak pressure is achieved. Symptoms along with flowmetry and residual urine were evaluated. Results: We present results of 12 patients: 7 TVT and 5 TOT. All were seen with urinary dysfunction and in all patients obstructive micturiction before the second surgery. Under spinal anaesthesia and with a bladder filled with 300 cc, 4 patients leaked with 60 cm and 8 with 80 cm of water pressure. Once the sling was sectioned it was adjusted to an IOLP of 35 cm of water. Symptoms and urodynamic studies showed recovery (11/12). Conclusion: Patients with OM alter SL showed high IOLP. Sling adjustment for a 35 cm water valsalva leak pressure delivers good postoperative results. SL section is an adequate treatment for these patients, urethrolysis seems questionable.

[Renal angiomyolipoma rupture as a cause of lumbar pain: report of one case]. / Angiomiolipoma renal complicado como causa de dolor lumbar: Caso clínico.

Renal angiomyolipoma is a benign tumor formed by smooth muscle, adipose tissue and blood vessels. It is commonly found incidentally and its clinical manifestations are pain and abdominal mass or spontaneous tumor rupture with retroperitoneal bleeding. The clinical presentation of a hemorrhagic shock secondary to a retroperitoneal hematoma is uncommon. We report a 40 year-old male who presented to the emergency room with lumbar pain and deterioration of hemodynamic parameters. The CT scan showed a left renal injury associated to an expansive retroperitoneal process. The abdominal exploration, vascular control of the renal pedicle and nephrectomy allowed a successful outcome.

Angiomiolipoma renal complicado como causa de dolor lumbar: caso clínico / Renal angiomyolipoma rupture as a cause of lumbar pain: report of one case

Renal angiomyolipoma is a benign tumor formed by smooth muscle, adipose tissue and blood vessels. It is commonly found incidentally and its clinical manifestations are pain and abdominal mass or spontaneous tumor rupture with retroperitoneal bleeding. The clinical presentation of a hemorrhagic shock secondary to a retroperítoneal hematoma is uncommon. We report a 40 year-old male who presented to the emergency room with lumbar pain and deteríoration of hemodynamic parameters. The CT sean showed a left renal injury associated to an expansive retroperítoneal process. The abdominal exploration, vascular control of the renal pedicle and nephrectomy allowed a successful outcome.

Uso de malla de polipropileno subalbugínea en orquiectomía bilateral por cáncer de próstata / Use of a testicular intralbugineal polypropylene mesh in bilateral orchiectomy for prostate cancer

Se presenta la experiencia del Servicio de Urología del Hospital Carlos Van Büren en el uso de malla de polipropileno intralbugínea como prótesis testicular, contemporánea a la orquiectomía subalbugínea bilateral por cáncer de próstata. Nuestra serie es de 30 pacientes, con un total de 60 testículos, correspondientes al período comprendido entre noviembre de 2001 y septiembre de 2002. Los resultados iniciales son alentadores.