Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Benzil/triethylamine: a photo-reducing system for Cu2.

ABSTRACT: Abstract:We have investigated the photo-induced reduction of Cu2+-Cu0 using benzil/triethylamine mixtures. The formation of elemental Cu is indicated by the appearance of its characteristic plasmon absorption peaks at 515 nm and 620 nm. Importantly, the nature of the counterion of the Cu2+ salt affects the reduction process. In the presence of Cl-, the reduction proceeds faster than with SO42-. Photo-induced electron transfer between excited benzil and triethylamine leads to the benzil radical anion, which acts as the reducing agent for Cu2+ and generates Cu0. Graphical abstract:

SUBMITTER: Schmallegger M

PROVIDER: S-EPMC5859703 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Benzil/triethylamine: a photo-reducing system for Cu2.

Schmallegger Max M Gescheidt Georg G

Monatshefte fur chemie 20180203 3

<h4>Abstract</h4>We have investigated the photo-induced reduction of Cu2+-Cu0 using benzil/triethylamine mixtures. The formation of elemental Cu is indicated by the appearance of its characteristic plasmon absorption peaks at 515 nm and 620 nm. Importantly, the nature of the counterion of the Cu2+ salt affects the reduction process. In the presence of Cl-, the reduction proceeds faster than with SO42-. Photo-induced electron trans ...[more]

PMID: 29576659

Similar Datasets

Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from CuICuICuI to CuIICuIICuII states.

Project description:One-pot reaction of tris(2-aminoethyl)amine (TREN), [CuI(MeCN)4]PF6, and paraformaldehyde affords a mixed-valent [TREN4CuIICuICuI(μ3-OH)](PF6)3 complex. The macrocyclic azacryptand TREN4 contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu3(μ3-OH)]3+ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [TREN4CuIICuICuI(μ3-OH)](PF6)3 exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [TREN4CuIICuICuI(μ3-OH)](PF6)3 and its solvent-exposed analog [TREN3CuIICuIICuII(μ3-O)](PF6)4 suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [TREN4CuICuICuI(μ3-OH)](PF6)2 can reduce O2 under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature's multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at CuICuICuI (4a), CuIICuICuI (4b), and CuIICuIICuI (4c) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (105 to 106 M-1 s-1) were observed for both CuICuICuI/CuIICuICuI and CuIICuICuI/CuIICuIICuI redox couples, approaching the rapid electron transfer rates of copper sites in MCO.

| S-EPMC8179370 | biostudies-literature

Benzil bis-(ketazine).

Project description:The title compound (systematic name1,1',2,2'-tetra-phenyl-2,2'-azinodiethanone), C(28)H(20)N(2)O(2), was obtained by the reaction of benzil monohydrazone with chromium(III) nitrate. The dibenzyl-idene hydrazine unit is nearly planar (r.m.s. deviation = 0.073?Å) and the two benzoyl units are oriented almost perpendicular to it [dihedral angle = 87.81?(2), 87.81?(2)°]. The mol-ecules are linked into chains along the c axis by C-H?O hydrogen bonds and the chains are cross-linked via C-H?? inter-actions involving the benzoyl phenyl rings.

| S-EPMC2977460 | biostudies-literature

Cu2+ coordination-induced in situ photo-to-heat on catalytic sites to hydrolyze β-lactam antibiotics pollutants in waters.

Project description:For degradation of β-lactam antibiotics pollution in waters, the strained β-lactam ring is the most toxic and resistant moiety to biodegrade and redox-chemically treat among their functional groups. Hydrolytically opening β-lactam ring with Lewis acid catalysts has long been recognized as a shortcut, but at room temperature, such hydrolysis is too slow to be deployed. Here, we found when Cu2+ was immobilized on imine-linked COF (covalent organic framework) (Cu2+/Py-Bpy-COF, Cu2+ load is 1.43 wt%), as-prepared composite can utilize the light irradiation (wavelength range simulated sunlight) to in situ heat anchored Cu2+ Lewis acid sites through an excellent photothermal conversion to open the β-lactam ring followed by a desired full-decarboxylation of hydrolysates. Under 1 W/cm2 simulated sunlight, Cu2+/Py-Bpy-COF powders placed in a microfiltration membrane rapidly cause a temperature rising even to ~211.7 °C in 1 min. It can effectively hydrolyze common β-lactam antibiotics in waters and even antibiotics concentration is as high as 1 mM and it takes less than 10 min. Such photo-heating hydrolysis rate is ~24 times as high as under dark and ~2 times as high as Cu2+ homogenous catalysis. Our strategy significantly decreases the interference from generally coexisting common organics in waters and potential toxicity concerns of residual carboxyl groups in hydrolysates and opens up an accessible way for the settlement of β-lactam antibiotics pollutants by the only energy source available, the sunlight.

| S-EPMC10756305 | biostudies-literature

Recent Advances in 64Cu/67Cu-Based Radiopharmaceuticals.

Project description:Copper-64 (T1/2 = 12.7 h) is a positron and beta-emitting isotope, with decay characteristics suitable for both positron emission tomography (PET) imaging and radiotherapy of cancer. Copper-67 (T1/2 = 61.8 h) is a beta and gamma emitter, appropriate for radiotherapy β-energy and with a half-life suitable for single-photon emission computed tomography (SPECT) imaging. The chemical identities of 64Cu and 67Cu isotopes allow for convenient use of the same chelating molecules for sequential PET imaging and radiotherapy. A recent breakthrough in 67Cu production opened previously unavailable opportunities for a reliable source of 67Cu with high specific activity and purity. These new opportunities have reignited interest in the use of copper-containing radiopharmaceuticals for the therapy, diagnosis, and theranostics of various diseases. Herein, we summarize recent (2018-2023) advances in the use of copper-based radiopharmaceuticals for PET, SPECT imaging, radiotherapy, and radioimmunotherapy.

| S-EPMC10288943 | biostudies-literature

A digital twin for 64Cu production with cyclotron and solid target system.

Project description:One method for finding reliable and cost-effective solutions for designing radioisotope production systems is represented by the "digital twin" philosophy of design. Looking at cyclotron solid targets, uncertainties of the particle beam, material composition and geometry play a crucial role in determining the results. The difference between what has been designed and what can be effectively manufactured, where processes such as electroplating are poorly controllable and generate large non-uniformities in deposition, must also be considered. A digital twin, where the target geometry is 3D scanned from real models, can represent a good compromise for connecting "ideal" and "real" worlds. Looking at the 64Ni(p,n)64Cu reaction, different Unstructured-Mesh MCNP6 models have been built starting from the 3D solid target system designed and put into operation by COMECER. A characterization has been performed considering the designed ideal target and a 3D scan of a real manufactured target measured with a ZEISS contact probe. Libraries and physics models have been also tested due to limited cross-section data. Proton spectra in the target volume, 3D proton-neutron-photon flux maps, average energies, power to be dissipated, shut-down dose-rate, 64Cu yield compared with various sources of experimental data and beam axial shifting impact, have been estimated. A digital twin of the 64Ni(p,n)64Cu production device has been characterized, considering the real measured target geometry, paving the way for a fully integrated model suitable also for thermal, structural or fluid-dynamic analyses.

| S-EPMC9653460 | biostudies-literature

Harnessing 64Cu/67Cu for a theranostic approach to pretargeted radioimmunotherapy.

Project description:Over the past decade, theranostic imaging has emerged as a powerful clinical tool in oncology for identifying patients likely to respond to targeted therapies and for monitoring the response of patients to treatment. Herein, we report a theranostic approach to pretargeted radioimmunotherapy (PRIT) based on a pair of radioisotopes of copper: positron-emitting copper-64 (64Cu, t 1/2 = 12.7 h) and beta particle-emitting copper-67 (67Cu, t 1/2 = 61.8 h). This strategy is predicated on the in vivo ligation between a trans-cyclooctene (TCO)-bearing antibody and a tetrazine (Tz)-based radioligand via the rapid and bioorthogonal inverse electron-demand Diels-Alder reaction. Longitudinal therapy studies were conducted in a murine model of human colorectal carcinoma using an immunoconjugate of the huA33 antibody modified with TCO (huA33-TCO) and a 67Cu-labeled Tz radioligand ([67Cu]Cu-MeCOSar-Tz). The injection of huA33-TCO followed 72 h later by the administration of 18.5, 37.0, or 55.5 MBq of [67Cu]Cu-MeCOSar-Tz produced a dose-dependent therapeutic response, with the median survival time increasing from 68 d for the lowest dose to >200 d for the highest. Furthermore, we observed that mice that received the highest dose of [67Cu]Cu-MeCOSar-Tz in a fractionated manner exhibited improved hematological values without sacrificing therapeutic efficacy. Dual radionuclide experiments in which a single administration of huA33-TCO was followed by separate injections of [64Cu]Cu-MeCOSar-Tz and [67Cu]Cu-MeCOSar-Tz revealed that the positron emission tomography images produced by the former accurately predicted the efficacy of the latter. In these experiments, a correlation was observed between the tumoral uptake of [64Cu]Cu-MeCOSar-Tz and the subsequent therapeutic response to [67Cu]Cu-MeCOSar-Tz.

| S-EPMC7668034 | biostudies-literature

Exogenous 2-(3,4-Dichlorophenoxy) triethylamine alleviates salinity stress in maize by enhancing photosynthetic capacity, improving water status and maintaining K+/Na+ homeostasis.

Project description:BackgroundSoil salinity restricts plant growth and productivity. 2-(3,4-dichlorophenoxy) triethylamine (DCPTA) can alleviate salinity stress in plants. However, the mechanism of DCPTA-mediated salinity tolerance has not been fully clarified. We aimed to investigate its role in enhancing photosynthetic capacity, improving water status, maintaining K+/Na+ homeostasis and alleviating salinity stress in maize (Zea mays L.).ResultsIn present study, maize seedlings were grown in nutrient solutions with a combination of NaCl (0, 150 mM) and DCPTA (0, 20, 100, and 400 μM). And photosynthesis, water status, ion homeostasis and the expression of genes involved in ion uptake and transport were evaluated in the maize seedlings. The results demonstrated that DCPTA alleviated the growth inhibition of maize seedlings exposed to salinity stress by increasing the net photosynthetic rate (Pn) and the quantum efficiency of photosystem II (PSII) photochemistry. DCPTA improved the root hydraulic conductivity, which help maintained the water status. A relatively high K+ concentration but a relatively low Na+ concentration and the Na+/K+ ratio were observed in the presence of DCPTA under salinity stress. Additionally, DCPTA altered the expression of four genes (ZmSOS1, ZmHKT1, ZmNHX1 and ZmSKOR) that encode membrane transport proteins responsible for K+/Na+ homeostasis.ConclusionsDCPTA improved the salinity tolerance of maize may be associated with enhanced photosynthetic capacity, maintenance of water status and altered expression of genes involved in ion uptake and transport.

| S-EPMC7376668 | biostudies-literature

Alkyne-tagged SERS nanoprobe for understanding Cu+ and Cu2+ conversion in cuproptosis processes.

Project description:Simultaneously quantifying mitochondrial Cu+ and Cu2+ levels is crucial for evaluating the molecular mechanisms of copper accumulation-involved pathological processes. Here, a series of molecules containing various diacetylene derivatives as Raman reporters are designed and synthesized, and the alkyne-tagged SERS probe is created for determination Cu+ and Cu2+ with high selectivity and sensitivity. The developed SERS probe generates well-separated distinguishable Raman fingerprint peaks with built-in corrections in the cellular silent region, resulting in accurate quantification of Cu+ and Cu2+. The present probe demonstrates high tempo-spatial resolution for real-time imaging and simultaneously quantifying mitochondrial Cu+ and Cu2+ with long-term stability benefiting from the probe assembly with designed Au-C≡C groups. Using this powerful tool, it is found that mitochondrial Cu+ and Cu2+ increase during ischemia are associated with breakdown of proteins containing copper as well as conversion of Cu+ and Cu2+. Meanwhile, we observe that parts of Cu+ and Cu2+ are transported out of neurons by ATPase. More importantly, cuproptosis in neurons is found including the oxidative stress process caused by the conversion of Cu+ to Cu2+, which dominates at the early stage (<9 h), and subsequent proteotoxic stress. Both oxidative and proteotoxic stresses contribute to neuronal death.

| S-EPMC11018805 | biostudies-literature

Al/Cu-PILC as a Photo-Fenton Catalyst: Paracetamol Mineralization.

Project description:Pillared clays have shown to effectively catalyze the photo-Fenton process without the necessity of acidic conditions, which is a very attractive feature from the perspective of environmentally friendly processes, especially when high natural abundance of chemical elements are incorporated. In this work, the catalytic activity of Al/Cu interlayered pillared clays for the degradation and mineralization of paracetamol through a photo-Fenton-like process was investigated. Al/Cu-pillared clays were prepared by adding ane Al/Cu pillaring solution to a bentonite suspension. X-ray diffraction (XRD) confirmed the enlargement of the interlayer space of the clay provoked by the pillaring process and Al and Cu species in the prepared samples were verified by atomic absorption spectroscopy (AAS). The specific surface area of pure bentonite was 2-fold increased after the Al/Cu pillaring process. A synthetic paracetamol solution with an initial concentration of 100 ppm was prepared for the assessment of the activity of the prepared materials. Different catalyst concentrations were tested (0.2, 0.5, 0.75, and 1 g L-1) and the complete removal of paracetamol was achieved in all cases, but the highest mineralization rate (69.8 mg total organic carbon (TOC) gcat -1 h-1) corresponds to the catalyst loading of 0.5 g L-1. An ultraviolet-C (UVC) light source was employed, and no adjustment of the pH to acidic conditions was needed to achieve these results. Liquid chromatography coupled to mass spectroscopy (LC-MS) was employed to identify the reaction intermediates of paracetamol degradation. A proposed pathway for the oxidation of paracetamol molecule is presented. The effect of Cu content in the pillared clay and the stability and reusability of the catalyst were also assessed. The kinetic constants of paracetamol removal were 0.2318 and 0.0698 min-1, under photo-Fenton and UV + H2O2 processes, respectively.

| S-EPMC9281314 | biostudies-literature

Nanomolar Pulse Dipolar EPR Spectroscopy in Proteins: CuII-CuII and Nitroxide-Nitroxide Cases.

Project description:The study of ever more complex biomolecular assemblies implicated in human health and disease is facilitated by a suite of complementary biophysical methods. Pulse dipolar electron paramagnetic resonance spectroscopy (PDS) is a powerful tool that provides highly precise geometric constraints in frozen solutions; however, the drive toward PDS at physiologically relevant sub-μM concentrations is limited by the currently achievable concentration sensitivity. Recently, PDS using a combination of nitroxide- and CuII-based spin labels allowed measuring a 500 nM concentration of a model protein. Using commercial instrumentation and spin labels, we demonstrate CuII-CuII and nitroxide-nitroxide PDS measurements at protein concentrations below previous examples reaching 500 and 100 nM, respectively. These results demonstrate the general feasibility of sub-μM PDS measurements at short to intermediate distances (∼1.5 to 3.5 nm), and are of particular relevance for applications where the achievable concentration is limiting.

| S-EPMC7611071 | biostudies-literature