Ternary Copper Research Articles

Layered bismuthene forming the interfacial pathway for rapid charge transfer in CuNb13O33/g-C3N5 photocatalyst for enhancing ciprofloxacin degradation

The objective of the present research was to examine the usefulness of the photocatalytic degradation process in removing the ciprofloxacin drug from wastewater, which is difficult to remove from waterbodies. To tackle this difficulty, a ternary copper niobium oxide/carbon nitride/layered bismuthene heterostructure (CuNb13O33/g-C3N5-L-Bi) composite was developed by an intuitive solvothermal process. layered bismuthene (L-Bi) was prepared using a unique ball milling approach. According to the results of the characterization, adding L-Bi and g-C3N5 with a low band gap to the original band structure of CuNb13O33 makes it more efficient. After 120 min of irradiation, the modified CuNb13O33/g-C3N5-L-Bi sample significantly improved ciprofloxacin degradation, resulting in a degradation rate of 98 %. In addition, the impact of the catalyst that has been created on the removal of ciprofloxacin at various pH, catalyst dosages, and scavengers was also examined, demonstrating the catalyst’s suitability for purifying natural water environments. A detailed study of the steps used to break down ciprofloxacin has shown that many active species are involved, with a focus on the important roles played by reactive oxidative species (ROS). Thus, this study introduces a novel combination of layered bismuthene photocatalysts for environmentally friendly degradation of antibiotics.

Bis(amino acidato)copper(II) compounds in blood plasma: a review of computed structural properties and amino acid affinities for Cu2+ informing further pharmacological research.

Neutral bis(amino acidato)copper(II) [Cu(aa)2] coordination compounds are the physiological species of copper(II) amino acid compounds in blood plasma taking the form of bis(l-histidinato)copper(II) and mixed ternary copper(II)-l-histidine complexes, preferably with l-glutamine, l-threonine, l-asparagine, and l-cysteine. These amino acids have three functional groups that can bind metal ions: the common α-amino and carboxylate groups and a side-chain polar group. In Cu(aa)2, two coordinating groups per amino acid bind to copper(II) in-plane, while the third group can bind apically, which yields many possibilities for axial and planar bonds, that is, for bidentate and tridentate binding. So far, the experimental studies of physiological Cu(aa)2 compounds in solutions have not specified their complete geometries. This paper provides a brief review of my group's research on structural properties of physiological Cu(aa)2 calculated using the density functional theory (DFT) to locate low-energy conformers that can coexist in aqueous solutions. These DFT investigations have revealed high conformational flexibility of ternary Cu(aa)2 compounds for tridentate or bidentate chelation, which may explain copper(II) exchange reactions in the plasma and inform the development of small multifunctional copper(II)-binding drugs with several possible copper(II)-binding groups. Furthermore, our prediction of metal ion affinities for Cu2+ binding with amino-acid ligands in low-energy conformers with different coordination modes of five physiological Cu(aa)2 in aqueous solution supports the findings of their abundance in human plasma obtained with chemical speciation modelling.

NH3 gas sensing and NH3-induced anti-counterfeiting based on nontoxic ternary copper halide

Lead-free ternary copper halides are emerging environmentally friendly materials, which have recently received great attention for their favorable optoelectronic properties. However, few attention was paid to their applications in gas sensing and gas-triggered fluorescence anti-counterfeiting. In this work, we demonstrate an effective Cs3Cu2I5 halide for NH3 sensing and NH3-triggered fluorescence anti-counterfeiting applications. The Cs3Cu2I5-based electrical NH3 sensor exhibits exceptional sensing performance, in which a resistance response of 77.8 % is achieved at 50 ppm NH3 with a rapid response time (9 s). To elucidate the NH3 sensing mechanism, we investigated the NH3-induced optical and structural evolutions including absorption, photoluminescence (PL), and Raman spectra. Our findings suggest that NH3 molecules, acting as electron donors, adsorb on the Cs3Cu2I5 surface, inducing the decomposition of Cs3Cu2I5 into CsCu2I3 and CsI. During this process, the CsCu2I3·NH3 intermediate phase is generated as a shell layer onto the surface of Cs3Cu2I5 grain, leading to an increase in electrical conductivity (or decrease in resistance), and an emission of bright yellow-red fluorescence from CsCu2I3. Inspired by NH3-induced fluorescence emission, we also explored a novel gas-triggered anti-counterfeiting method using Cs3Cu2I5-paper, demonstrating favorable reversibility and convenience, compared to previously reported water-triggered anti-counterfeiting techniques. This work will promote the development of design of Cs3Cu2I5 for gas sensing and gas-triggered fluorescence anti-counterfeiting applications in the future.

Effect of Sb2S3 sacrificial layer thickness on structural, optical and electrical properties of CuSbS2 films and investigation of diode parameters of CuSbS2/CdS heterojunctions

The ternary copper chalcogenides CuSbS2 (CAS) is found to have appealing optical and photovoltaic properties to be used as absorber layer in thin film solar cells. However, the difficulty to grow good quality CuSbS2 layer of micrometer thickness by chemical bath deposition method holds a big challenge. In this work, we reported the effect of incorporating Sb2S3 sacrificial layer of different thickness on structural, optical and electrical properties of CAS films. The X-ray diffraction results and Raman spectroscopic analysis confirm the formation of single-phase orthorhombic crystal structure for CuSbS2. The increase of Sb content in CAS films with the increase in deposition time of Sb2S3 layer has been reflected in the change in relative intensity ratio of characteristic Raman peaks as well as in diffraction peak profiles. The magnitude of defect states in terms of Urbach energy is decreased drastically by increasing Sb percentage in the films. A clear improvement in electrical properties of CAS films is observed with the decrease in Cu/Sb ratio. The carrier density is increased by one order of magnitude from 1016 to 1017 cm−3 and hole mobility increases from 1.14 to 4.87 cm2/Vs. The impact of Sb concentration on Scottky diode parameters of CAS/CdS heterojunction was studied by using thermionic emission model. Both the ideality factor and series resistance are decreased with the increase in Sb content. The J-V measurements reveal that the integration of Sb2S3 sacrificial layer improves the PV parameters such as fill factor, open circuit voltage, photocurrent and efficiency. The overall improvement in diode parameters can be ascribed to decrease in defect states, better film quality, absorber layer thickness and improved stoichiometry of CAS films.

Ternary Copper(II) Coordination Compounds with Nonpolar Amino Acids and 2,2′-Bipyridine: Monomers vs. Polymers

Reactions of copper(II) sulfate with 2,2′-bipyridine (bipy) and amino acids with nonpolar side chains (l-alanine (HAla), l-valine (HVal), or l-phenylalanine (HPhe)) were investigated under different solution-based and mechanochemical methods. Five new ternary coordination compounds were obtained by a solution-based synthesis and three of them additionally by the liquid-assisted mechanochemical method: {[Cu(μ-l-Ala)(H2O)(bipy)]2SO4·2H2O}n (1a·2H2O), {[Cu(μ-l-Ala)(H2O)(bipy)][Cu(l-Ala)(H2O)(bipy)]SO4·2.5H2O}n (1b·2.5H2O), {[Cu(μ-l-Val)(H2O)(bipy)][Cu(l-Val)(H2O)(bipy)]3(SO4)2·4H2O}n (2·4H2O), [Cu(l-Phe)(H2O)(bipy)][Cu(l-Phe)(SO4)(bipy)]∙8H2O (3·8H2O), and [Cu(l-Phe)(H2O)(bipy)][Cu(l-Phe)(SO4)(bipy)]∙9H2O (3·9H2O). The compounds were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, and a thermal analysis. Structural studies revealed two structural types, monomeric in 3·8H2O and 3·9H2O, polymeric architectures in 1a·2H2O, and mixed structures (monomeric and polymeric) in 1b·2.5H2O and 2·4H2O. The copper(II) ion is either pentacoordinated or hexacoordinated, with an observed Jahn–Teller effect. The crystal structures are based on an intensive network of hydrogen bonds and π interactions. 1a·2H2O and 2·4H2O showed substantial in vitro antiproliferative activity toward human hepatocellular carcinoma (HepG2) and moderate activity toward human acute monocytic leukemia cell lines (THP-1).

Self-Powered Visible-Blind Ultraviolet Photodetector Based on Organic-Inorganic Hybrid Copper Halide [N(C2H5)4]2[Cu2Br4

Organic-inorganic hybrid ternary copper halides offer a broader spectrum of structural possibilities for finely tuning their optoelectronic properties. Herein, we demonstrate for the first time the potential of [N(C2H5)4]2[Cu2Br4], a zero-dimensional hybrid copper halide [(TEA)2Cu2Br4], for ultraviolet (UV) photodetection. A self-powered, visible-blind UV photodetector based on a (TEA)2Cu2Br4/GaN heterojunction architecture is developed, exhibiting a high responsivity, a high detectivity, and fast response speeds. The device demonstrates exceptional stability against environmental oxygen/moisture, heat, and UV light illumination, surpassing the stability of reported copper-based UV photodetectors. Our work highlights the significant potential of (TEA)2Cu2Br4 as a lead-free, stable, and efficient material for next-generation UV photodetection technology.

Efficient Large-Area (81 cm2) Ternary Copper Halides Light-Emitting Diodes with External Quantum Efficiency Exceeding 13% via Host-Guest Strategy.

Ternary copper (Cu) halides are promising candidates for replacing toxic lead halides in the field of perovskite light-emitting diodes (LEDs) toward practical applications. However, the electroluminescent performance of Cu halide-based LEDs remains a great challenge due to the presence of serious nonradiative recombination and inefficient charge transport in Cu halide emitters. Here, the rational design of host-guest [dppb]2Cu2I2 (dppb denotes 1,2-bis[diphenylphosphino]benzene) emitters and its utility in fabricating efficient Cu halide-based green LEDs that show a high external quantum efficiency (EQE) of 13.39% are reported. The host-guest [dppb]2Cu2I2 emitters with mCP (1,3-bis(N-carbazolyl)benzene) host demonstrate a significant improvement of carrier radiative recombination efficiency, with the photoluminescence quantum yield increased by nearly ten times, which is rooted in the efficient energy transfer and type-I energy level alignment between [dppb]2Cu2I2 and mCP. Moreover, the charge-transporting mCP host can raise the carrier mobility of [dppb]2Cu2I2 films, thereby enhancing the charge transport and recombination. More importantly, this strategy enables a large-area prototype LED with a record-breaking area up to 81 cm2, along with a decent EQE of 10.02% and uniform luminance. It is believed these results represent an encouraging stepping stone to bring Cu halide-based LEDs from the laboratory toward commercial lighting and display panels.

Synthesis and characterization of CuxCd1‐xS nanocrystals into functionalized nitrile butadiene rubber matrix

AbstractIntroductionPolymetallic sulfides and heterostructures like CdIn2S4, CdZnS2, CuxS‐NiySz, Cu2CoSnS4, CoNi2S4, Zn0.76Co0.24S have been fabricated with various shapes and forms for new applications. Ternary copper cadmium sulfides (CuCdS2) are a p‐type semiconductor with a direct band gap of about 2.4 eV forms very good nanocrystals like copper sulfide could be potentially applied to optical and electronic applications. Knowing that the SILAR synthesis, optical, paramagnetic, dielectric properties, and annealing of copper cadmium sulfides have not been sufficiently investigated, they are extensively analyzed and studied in the present work.ObjectivesCuxCd1−xS (x = 0, 0.5, and 1) nanoparticles have been synthesized on the base of functionalized nitrile butadiene rubber by SILAR method and characterized using scanning electron microscopy, x‐ray diffractometer, UV–visible spectroscopy, Fourier‐transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy. Effects of cycles, reaction time, and precursor concentration on the particle size, crystal growth and structure, bandgap energy, dielectric and paramagnetic properties, elemental composition, and morphology were investigated.MethodsThe synthesis of CuxCd1−xS nanocrystals was carried out into the obtained functional polymer matrix by SİLAR method. The functional polymer (FNBR) is a dark brown powder which contains ‐PO(OH)2 and ‐OPO(OH)2 functional groups and does not dissolve in organic and inorganic solvents, can be used as a very good stabilizer of nanostructures. The synthesis of CuxCd1−xS/FNBR nanocompsite was carried out in 3, 5, and 15 cycles.Results and discussionIn the process of ternary sulfide formation, the nucleation rate of CdS was high at the beginning of the reaction, while the growth rate and stability of CuS were high in the later course of the reaction. The average crystallite size of the nancrystallites has been increased from 1.13 nm to 7.39 nm by the increasing of the number of cycles from 5 to 15, respectively. It is explained by the inclusion of copper in the composition and getting more stable material. Copper cadmium sulfide nanostructures demonstrate wide band gap energy (~3.7 eV) in this work which is explained by the formation of nanosized particles in a limited volume of FNBR matrix.ConclusionsThe synthesis of CuxCd1‐xS nanocrystals was carried out into the obtained functional polymer matrix by SİLAR method. Strong diffraction peaks corresponding to cubic CdS are found with low SILAR cycles. SEM images of CuxCd1−xS/FNBR nanocomposite show that the atomic percentage of Cu and Cd into the ternary sulfide is 20.19% and 0.61%, respectively. It is explained by the inclusion of copper in the composition and getting more stable material with low solubility products (Ksp) which is in good agreement with XRD results. The calculated band gaps are higher than that of bulk CdS, CuS, and CuCdS2. Larger band gap is usually reported for defects or structural disorders, which is in good agreement with XRD and Raman results.

Analyzing the Precipitation Effects in Low-Alloyed Copper Alloys Containing Hafnium and Chromium

Copper alloys containing chromium and hafnium combine elevated mechanical strength and high electrical and thermal conductivity. For the simultaneous enhancement of both material properties, precipitation hardening is the utilized mechanism. Therefore, the aim is to analyze the influence of chromium and hafnium in binary and ternary low-alloyed copper alloys and to compare the precipitation processes during temperature exposure. Atom probe tomography (APT) and differential scanning calorimetry (DSC) measurements enable to understand the precipitation sequence in detail. CuCr0.7 starts to precipitate directly, whereas CuHf0.7 is highly influenced by prior diffusion facilitating cold rolling. Within the ternary alloy, hafnium atoms accumulate at the shell of mainly Cr-containing precipitates. Increasing the local hafnium concentration results in the formation of intermetallic CuHf precipitates at the sites of mainly Cr-containing precipitates. Indirect methods are utilized to investigate the materials’ properties and show the impact of cold rolling prior to an aging treatment on binary alloys CuCr and CuHf. Finally, ternary alloys combine the benefits of facilitated precipitation processes and decelerated growing and coarsening, which classifies the alloys to be applicable for usage at elevated temperatures.

Simplified LIBS-based intensity-ratio approach for concentration estimation (SLICE): an approach for elemental analysis using laser induced breakdown spectroscopy.

We propose what we believe to be a new approach for elemental analysis using laser induced breakdown spectroscopy (LIBS). This method offers enhanced convenience and simplicity for elemental analysis as it eliminates the necessity of Boltzmann/ Saha-Boltzmann plot. It is an intensity-ratio based approach that provides several notable advantages. One of the key benefits is its ability to perform comprehensive elemental analysis using only a few spectral lines; specifically, only n + 1 emission lines are sufficient for a sample containing n elemental species. This offers a great flexibility in the choice of emission lines which do not suffer from self-absorption. Further, high accuracy can be obtained as many repeated estimations from a single measurement are possible. We demonstrate the theory and working procedure of this technique by experimentally recording the data of two samples (binary and ternary copper alloys). A nanosecond Nd:YAG pulsed laser of ∼7 ns pulse duration and 532 nm incident wavelength is used. The results are in good agreement with CF-LIBS and Energy-dispersive X-ray spectroscopy (EDS).

Modeling and optimization of numerical studies on CuSbS2 thin film solar cell with ∼ 15% efficiency

In this paper, the Silvaco TCAD simulation tool is utilized for modeling of ternary chalcostibite copper antimony sulfide (CuSbS2) thin film solar cells (TFSCs). The earth-abundant CuSbS2 is a promising material as a solar absorber and hole transport layer due to its high optical absorption coefficient, and low cost. CuSbS2 based solar cell can be fabricated in vacuum-free environment. Mostly CdS is used as electron transport layer (ETL) in CuSbS2 based solar cell but the efficiency is low due to creation of Schottky barrier at the back-contact and substantial carrier recombination at the CuSbS2/CdS interface. Hence, a (ITO/n-TiO2/p-CuSbS2/Au) np heterojunction-based solar cell has been developed. The observed maximum power conversion efficiency (PCE) of 15.26% (open circuit voltage (Voc) = 823 mV, short circuit current (Jsc) = 28.48 mA/cm2, fill factor (FF) = 65.1%) is achieved by optimizing the absorber thickness (400 nm) of the solar cell. Different parameters like effect of absorber thickness, back contact, bandgap, carrier concentration, temperature, and defect density are optimized to find the best possible efficiency of the solar cell. The device also exhibits good performance stability at high temperatures. Based on results, a (ITO/n-TiO2/p-CuSbS2/Au) np heterojunction-based fabricated solar cell device is possible in future.

Progress and applications of (Cu–)Ag–Bi–I semiconductors, and their derivatives, as next-generation lead-free materials for photovoltaics, detectors and memristors

The search for efficient but inexpensive photovoltaics over the past decade has been disrupted by the advent of lead-halide perovskite solar cells. Despite impressive rises in performance, the toxicity and stability concerns of these materials have prompted a broad, interdisciplinary community across the world to search for lead-free and stable alternatives. A set of such materials that have recently gained attention are semiconductors in the CuI–AgI–BiI3 phase space and their derivatives. These materials include ternary silver bismuth iodide compounds (Ag aBi bI a+3 b), ternary copper bismuth iodide Cu–Bi–I compounds and quaternary Cu–Ag–Bi–I materials, as well as analogues with Sb substituted into the Bi site and Br into the I site. These compounds are comprised of a cubic close-packed sub-lattice of I, with Ag and Bi occupying octahedral holes, while Cu occupies tetrahedral holes. The octahedral motifs adopted by these compounds are either spinel, CdCl2-type, or NaVO2-type. NaVO2-type Ag aBi bI a+3 b compounds are also known as rudorffites. Many of these compounds have thus far demonstrated improved stability and reduced toxicity compared to halide perovskites, along with stable bandgaps in the 1.6–1.9 eV range, making them highly promising for energy harvesting and detection applications. This review begins by discussing the progress in the development of these semiconductors over the past few years, focusing on their optoelectronic properties and process–property–structure relationships. Next, we discuss the progress in developing Ag–Bi–I and Cu–Bi–I compounds for solar cells, indoor photovoltaics, photodetectors, radiation detectors and memristors. We conclude with a discussion of the critical fundamental questions that need to be addressed to push this area forward, and how the learnings from the wider metal-halide semiconductor field can inform future directions.

Rapid continuous aqueous production of copper indium sulfide quantum dots via a microwave-assisted microfluidic technique.

Ternary copper indium sulfide (CIS) quantum dots (QDs) have been emerging as attractive alternatives to Cd- and Pb-based QDs in various applications owing to their favorable optical properties and low toxicity. However, methods allowing continuous production of CIS QDs in an easy-to-perform and/or organic-solvent-free way are yet to be realized. Here, we report a facile, rapid, continuous, and aqueous synthetic approach for CIS QDs based on a microwave-assisted microfluidic (MAM) technique with easy scale-up of production. Typically, CIS QDs and CIS@ZnS QDs are continuously produced with a flow rate of 30 mL h-1 at a moderate temperature (∼95 °C) in an open-air system with a continuous flow of water as the reaction medium. This continuous synthesis process circumvents the requirements of batch operation, a degassed/inert atmosphere, high temperatures, organic solvents, and complex/expensive equipment. The resulting water-soluble CIS@ZnS QDs show a photoluminescence quantum yield of 44%. This work provides an efficient and green synthetic route for the scalable production of fluorescent nanomaterials.

A study on the quantitative recrystallization of cold deformed copper affected by tin-lead solder

It has been observed that the fractional recrystallization characteristics of commercially pure copper is affected by the presence of individual or both the constituent elements of the Sn-Pb solder alloy. In order to design the experiment, commercially pure Cu, binary copper alloys (Cu-Sn and Cu-Pb) and ternary copper alloy, Cu-Sn-Pb are investigated. Cast alloys are homogenized, solution treated, and then quenched to complete the thermal treatment. In order to recrystallize, alloys are cold rolled to a 75% thickness and then annealed at 700°K isothermally for varying durations, up to 3600 seconds. In this experiment, the fractional recrystallization of annealed samples is evaluated as the normalized difference in microhardness recorded at various time steps. Additionally, in an attempt to verify the experimental results, the well-known Johnson-Mehl-Avrami-Kolmogorov equation is also used to predict the associated recrystallization behavior. From the study, it can be inferred that the presence of Sn-Pb solder-alloy elements have a positive impact on the recrystallization behavior of pure copper due to the solid solution strengthening, in which the effect of tin is greater than that of lead. Quantitative analysis indicates that recrystallization of pure Cu, Cu-Sn, Cu-Pb, and Cu-Sn-Pb alloys attains 99.4%, 95.4%, 98.4%, and 89.5%, respectively. Sn forms intermetallic with Cu but Pb does not. Additionally, Sn forms different intermetallic with impurities and has a BCC crystal structure dissimilar to the FCC of Cu and Pb. As a result, the formation of GP zones and the intermetallic phases during annealing show greater differences in the recrystallization behavior between the two approaches. By combination, microstructural studies of the cold-rolled alloys reveal the elongated grains of the second phases, and the alloys almost completely re-crystallized after 1800 seconds of annealing at 700°K.

Exploring the BSA- and DNA-binding, cytotoxicity, and cell cycle evaluation of ternary copper(II)/diimine complexes with N,N-dibenzyl-N'-benzoylthiourea as promising metallodrug candidates.

Four new copper(II) complexes were synthesized and characterized with the general formula [Cu(N-N)(Th)(NO3)], where N-N corresponds to the N-heterocyclic ligands 1,10-phenanthroline (phen), 2,2'-bipyridine (bipy), 4,7-diphenyl-1,10-phenanthroline (dpp), and 4,4-dimethyl-2,2'-bipyridine (dmbp) and Th represents the N,N-dibenzyl-N'-benzoylthiourea. Cytotoxic activities of the complexes against HCT116 (human colon carcinoma), HepG2 (human hepatocellular carcinoma), and non-tumor MRC-5 (human lung fibroblast) cells were investigated. The copper(II) complexes 1-4 were characterized by spectroscopic techniques while complexes 1 and 2 were studied using single-crystal X-ray diffraction as well. The complexes possessed a five-coordinated structure with one nitrate ligand as a monodentate at the axial position and two bidentate ligands N-heterocyclic and N,N-dibenzyl-N'-benzoylthiourea. The complexes showed promising IC50 values, ranging from 0.3 to 9.0 μM. Furthermore, interaction studies with biomolecules such as calf thymus DNA (ct-DNA) and Bovine Serum Albumin (BSA), which can act as possible biological targets of the complexes, were carried out. The studies suggested that the compounds interact moderately with ct-DNA and BSA. Complexes 1, 2, and 4 did not lead to cell accumulation at any stage of the cell cycle but caused a significant increase in internucleosomal DNA fragmentation. Whereas, compound 3 caused cell cycle arrest in the S phase while doxorubicin caused cell cycle arrest in the G2/M phase. The effect of structural modifications on the metal compounds was correlated with their biological properties and it was concluded that an increase in biological activity occurred with increasing the extension of the diimine ligands. Thus, complex 3 was the most promising one.

Chemical analysis of bronze votives from the Minoan peak sanctuary at Ayios Yeoryios Sto Vouno, Kythera

The Minoan peak sanctuary at Ayios Yeoryios sto Vouno, Kythera, was founded in the MMIB period and reached its acme in the MMIIIB-LMIA period. Its special character is confirmed by the number and the variety of its bronze finds, which outnumber all similar finds made on Minoan peak sanctuaries. For this reason, a systematic study of the techniques used for their construction is being carried out, aiming at clarifying issues of bronze provenance, circulation and use during the apogee of Minoan civilization.The paper presents the preliminary results of micro-XRF and SEM-EDS techniques applied on two categories of bronze finds from the sanctuary, namely 48 figurines and 59 blade cut-outs, in order to clarify their chemical composition and the type of the alloy used for their manufacturing, and also to examine possible particularities of their technological characteristics. It was revealed that alloys with a high copper content or pure copper with a small amount of impurities had been used in the production of bronze votives. Although copper is the dominant component, tin, lead, arsenic and iron are also present in various concentrations; elements such as nickel, cobalt, zinc, selenium, bismuth, silver and antimony are recorded in minor or trace amounts, as detected in areal or linear analyses. Different alloys depending on the manufacturing technique had been used. Leaded copper and ternary copper alloys of Cu-Sn-Pb were identified in the figurine category, while in the blade category the examined objects were mostly manufactured of pure copper, of about 98%wt and above. Binary copper-tin alloy has been used only in few objects. Copper containing minor constituents may be due either to recycling or to their initial presence in the ore.

Structure prediction of physiological bis(amino acidato)copper(II) species in aqueous solution: The copper(II) compounds with l-glutamine and l-histidine

Neutral (l-histidinato)(l-glutaminato)copper(II) [Cu(His)(Gln)] has been established as the most abundant ternary copper(II) amino acid compound of the exchangeable copper(II) pool in blood plasma. The experimental studies of Cu(His)(Gln) and bis(glutaminato)copper(II) [Cu(Gln)2] in solutions did not specify their complete geometries. To determine the geometries, this paper investigates the conformers, energy landscapes, and a structure–magnetic parameters relation of Cu(Gln)2 and Cu(His)(Gln) by the density functional theory (DFT) calculations. We assume a glycine-like coordination of Gln (other coordination patterns are dismissed because of steric reasons), and three His in-plane copper(II) binding modes. The conformational analyses are performed in the gas phase and implicitly modeled aqueous solution. The reliability of the DFT relative electronic and Gibbs free energies of the Cu(His)(Gln) conformers is confirmed by benchmarking against the corresponding energies obtained by the domain-based local pair natural orbital coupled-cluster method with singles, doubles, and perturbative triples [DLPNO-CCSD(T)]. Several cis- and trans-Cu(His)(Gln) conformers with His in the histaminate-like and glycine-like modes have low Gibbs free energies, and the greatest estimated metal-binding affinities. The DFT-calculated magnetic parameters of the low-energy conformers reproduce best the experimental electron paramagnetic resonance parameters measured in aqueous solutions for trans- and cis-Cu(Gln)2 conformers having two oxygen atoms (either from Gln or water molecules) at the apical positions, and Cu(His)(Gln) conformers having His in the histaminate-like mode with an apically placed carboxylato oxygen atom. The predicted conformational flexibility of His‑copper(II)-amino acid compounds may be connected with their physiological abundance, and the role in copper(II) exchange reactions in blood plasma.

Heteroleptic Copper(II) Complexes Containing an Anthraquinone and a Phenanthroline as Synthetic Nucleases and Potential Anticancer Agents

Two ternary copper(II) complexes with an anthraquinone and a N,N-heterocyclic donor, [Cu(dmp)(L)(H2O)](ClO4) (1), [Cu(bpy)(L)(dmso)](ClO4) (2), in which dmp = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2′-bipyridine, and HL = 1-hydroxyanthracene-9,10-dione were synthesized and fully characterized by conductivity, elemental, and spectral analyses (FTIR and UV-Vis; EPR and ESI-MS). The structure of 1 reveals that Cu(II) is bound to two oxygens of L, two nitrogens of dmp, and a molecule of water in the fifth position. In complex 2.1, Cu(II) is also pentacoordinated with an O-bonded dmso in the axial position. The presence of the heteroleptic complexes in solution was evidenced by ESI-MS, EPR in dmso solution and UV-Vis spectrophotometry. All complexes bind to CT-DNA with affinity constants of approximately 104. Complex 2 can nick plasmid DNA but no cleavage was performed by complex 1. The investigation of DNA interactions by spectrofluorimetry using ethidium bromide (EB) showed that it was displaced from DNA sites by the addition of the complexes. The complexes inhibited the growth of chronic myelogenous leukemia and human squamous carcinoma cells with low IC50 values, complex 1 being the most effective.

Recent Advances and Opportunities of Eco‐Friendly Ternary Copper Halides: A New Superstar in Optoelectronic Applications (Adv. Mater. 44/2023)

Recent Advances and Opportunities of Eco‐Friendly Ternary Copper Halides: A New Superstar in Optoelectronic Applications (Adv. Mater. 44/2023)

Structural, Vibrational, Thermal, and Cytotoxic Characterization of Aqua(1,10‐Phenanthroline)(L‐Serinato)Copper(II) Nitrate Complex Combined with DFT Calculations

AbstractIn this study, X‐ray diffraction confirms the crystallization of aqua(1,10‐phenanthroline)(L‐serinato)copper(II) nitrate in the triclinic system (P‐1). Density functional theory calculations are used to assign the vibration bands of Cu2+ ion and phenanthroline (phen) and L‐serine (L‐ser) ligands obtained by Raman and Fourier‐transform infrared spectroscopy. Physical and analytical properties, evaluated by computational study utilizing CrystalExplorer software, show the prevalence of H···O/O···H interaction. Thermal analyses show that the complex is stable in the temperature interval of 300–390 K. For temperatures above 390 K, the elimination of coordinated water molecules (380–430 K), mass loss of serine (440–660 K), and material decomposition process above 660 K. The solubility of the complex in water reaches 21.4 mg mL−1 at 35 °C. Parameters of drug‐likeness and assessment of absorption, distribution, metabolism, and excretion (ADME) properties are calculated. The in vitro cytotoxic assays against the cancer cell line of the HCT‐116 type (human colorectal carcinoma) exhibits toxicity (IC50 = 1.88 µm and selectivity index of 2.17) for the complex. The results highlight the potential of ternary copper complexes such as [Cu(phen)(L‐ser)(H2O)]NO3 for anticancer drug development as attractive, efficient, and low‐cost materials.