Cupriphication of gold to sensitize d10–d10 metal–metal bonds and near-unity phosphorescence quantum yields

Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reductionuponcupriphicationofcyclic trinucleartrigonal-planargold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(μ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(μ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2, N3-MeIm)2Cu(μ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(μ3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(μ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(μ-3,5-(CF3)2Pz)]3, (2)} formuponreactingAu3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R =benzyl/methyl/ethyl =BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via twoAu(I)⋯Cu(I)metallophilicinteractions,whereas 4a exhibitsa hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligandunassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35– 43kcal/molbindingenergy,akintotypicalM–Msingle-bondenergies. Congruently, FTIR spectra of4a showmultiple far-IR bands within 65– 200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilicsensitizationinextinctioncoefficientandsolid-state photoluminescence quantum yields approaching unity (ΦPL = 0.90–0.97 vs. 0–0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications

Aspartames Alter Pharmacokinetics Parameters of Erlotinib and Gefitinib and Elevate Liver Enzymes in Wistar Rats

Background: Erlotinib (ERL) and gefitinib (GEF) are extensively metabolized by CYP450 enzymes. Aspartame (ASP), an artificial sweetener, induces CYP2E1 and CYP3A2 enzymes in the brain and could increase liver enzymes. In this work, the influence of ASP on the pharmacokinetics (PK) of ERL and GEF in Wistar rats was evaluated. Methods: The PKs of ERL and GEF were evaluated after receiving 175 mg/kg or 1000 mg/kg of ASP for four weeks using UPLC-MS/MS. Levels of liver enzymes after four weeks of ASP consumption were also evaluated. Results: ASP 175 mg/kg was able to significantly alter levels of Cmax (36% increase for ERL, 38% decrease for GEF), AUC0–72 (205% increase for ERL, 41% increase for GEF), and AUC0–∞ (112% increase for ERL, 14% increase for GEF). Moreover, ASP 175 mg/kg decreased the apparent oral clearance ERL and GEF by 58% and 13%, respectively. ASP 1000 mg/kg increased Cmax of ERL by 159% and decreased GEF’s Cmax by and 73%. Both AUC0–72 and AUC0–∞ were increased by ASP 1000 for ERL and decreased for GEF. CL/F decreased by 64% for ERL and increased by 38.8% for GEF. Moreover, data indicated that ASP significantly increased levels of liver enzymes within two weeks of administration. Conclusions: Although ASP 175 and 1000 mg/kg alter ERL and GEF PKs parameters, ASP 1000 mg/kg has the highest impact on most parameters. ASP 1000 mg/kg also can significantly increase activities of liver enzymes indicating the possibility of inducing liver injury. Therefore, it might be of clinical importance to avoid the administration of aspartame containing products while on ERL or GEF therapy

Direct patient costs associated with tuberculosis diagnosis in Yemen and Nepal

BACKGROUND: The diagnosis of TB requires multiple visits. Reducing the number of visits for diagnosis could make the process more accessible, with significant savings to the patients.OBJECTIVE: To describe direct costs incurred by patients consulting TB diagnostic centres.METHOD: Adults with cough &gt;3 weeks' duration were interviewed using structured questionnaires in Yemen and Nepal to quantify their expenses.RESULTS: A total of 456 adults were interviewed. Most patients were accompanied, and 20% were smear-positive. Patients in Nepal were more likely to be male, to live in urban areas and were older (123/206 [60%], 152 [74%] and mean age 41 years) than in Yemen (120/250 [48%], 114 [36%] and mean age 35 years). Although most patients from rural areas stayed with relatives, their overall expenses were higher than for patients from urban areas. Clinic fees represented the highest expenditure in both countries, and rural patients paid more than urban patients in both settings. The expenses for diagnosis were equivalent to 1 week of the national income per capita.CONCLUSION: Patients incur considerable costs for diagnosis, and clinic fees represent a substantial component of these costs. Patients requiring investigations for TB should be able to access diagnostic services free of charge.</p

Direct patient costs associated with tuberculosis diagnosis in Yemen and Nepal

BACKGROUND: The diagnosis of TB requires multiple visits. Reducing the number of visits for diagnosis could make the process more accessible, with significant savings to the patients.OBJECTIVE: To describe direct costs incurred by patients consulting TB diagnostic centres.METHOD: Adults with cough &gt;3 weeks' duration were interviewed using structured questionnaires in Yemen and Nepal to quantify their expenses.RESULTS: A total of 456 adults were interviewed. Most patients were accompanied, and 20% were smear-positive. Patients in Nepal were more likely to be male, to live in urban areas and were older (123/206 [60%], 152 [74%] and mean age 41 years) than in Yemen (120/250 [48%], 114 [36%] and mean age 35 years). Although most patients from rural areas stayed with relatives, their overall expenses were higher than for patients from urban areas. Clinic fees represented the highest expenditure in both countries, and rural patients paid more than urban patients in both settings. The expenses for diagnosis were equivalent to 1 week of the national income per capita.CONCLUSION: Patients incur considerable costs for diagnosis, and clinic fees represent a substantial component of these costs. Patients requiring investigations for TB should be able to access diagnostic services free of charge.</p

New Coordination Polymers of Copper(I) and Silver(I) with Pyrazine and Piperazine: A Step Toward “Green” Chemistry and Optoelectronic Applications

Five coordination polymers and one hexanuclear cluster have been obtained, and their crystal structures were determined upon reaction of Cu­(I) or Ag­(I) precursors with pyrazine (Pyz) or piperazine (Ppz). Five complexes are mixed-imine-ligand with anionic-fluorinated pyrazolate [3,5-(CF₃)₂Pz]⁻ ([Pz^F]⁻) besides Pyz or Ppz, whereas the sixth had the neutral diimine as a single chromophore. Complexes <b>1</b>–<b>3</b> are isomers of the same Cu/Pz^F/Pyz composition with the same or different unit cell stoichiometry, namely, {Cu₆[3,5-(CF₃)₂Pz]₆­(Pyz)₃­(CH₂Cl₂)}_∞ (<b>1</b>·CH₂Cl₂), {Cu₂[3,5-(CF₃)₂Pz]}₂­(Pyz)₂­·toluene}_∞ (<b>2</b>·toluene), and {Cu₃[3,5-(CF₃)₂Pz]₃­(Pyz)_1.5­·1.5benzene}_∞ (<b>3</b>·1.5benzene), respectively. Altering only the metal attains {Ag₆[3,5-(CF₃)₂Pz]₆­(Pyz)₂­·2benzene} (<b>4</b>·2benzene), while also changing the neutral diimine attains {Ag₂[3,5-(CF₃)₂Pz]₂­(Ppz)}_∞ (<b>5</b>). Using Pyz without an anionic imine yields {[Cu­(Pyz)­(MeCN)₂]­[BF₄]}_∞ (<b>6</b>). The crystal structure of <b>1</b> shows two trimers linked together with two pyrazine ligands. Crystals of <b>2</b> represent a metal–organic framework (MOF-TW1) with significant surface area (1278 m²/g) and porosity (23.7% void volume) without considering toluene adsorbates in channels. MOF-TW1 was obtained serendipitously upon a reaction attempt to attain a mixed-metal product, instead attaining a Cu­(I)-only product with interconnected four-coordinate dinuclear units. Likewise, <b>3</b> was obtained through a transmetalation of all Ag atoms in <b>4</b> to replace them by Cu atoms. Three reactions (to obtain <b>1</b>, <b>4</b>, and <b>5</b>) were successfully carried out by both solvent-mediated and solventless transformations, whereas <b>2</b> and <b>3</b> were obtained only by solvent-mediated reactions, while <b>6</b> was attainable only by solventless transformations. The solventless transformations occurred either by sublimation and vapor diffusion or by mechanical grinding at ambient laboratory conditionswithout the aid of heating, high pressure, vacuum, or any automated equipment. All transformations could be monitored by the human eye as the reaction progresses, as evidenced by progressive discoloration and/or luminescence changes. All crystal structures were obtained with the aid of conventional crystal growth methods from organic solvents for bulk products obtained from both solvelntless and solvent-mediated reactions. Powder X-ray diffraction was used to compare bulk products with one another and the crystallographic products. All Cu­(I) products are colored and nonluminescent; the progress of their vapor diffusion-based solventless reactions can be followed by gradual discoloration of white solid reactants and/or quenching precursor’s phosphorescence. Both Ag­(I) products were colorless with <b>4</b> being luminescent but not <b>5</b>

Pyrene Bearing Azo-Functionalized Porous Nanofibers for CO2 Separation and Toxic Metal Cation Sensing

This article describes the construction of a novel luminescent azo-linked polymer from 1,3,6,8-tetra(4--aminophenyl)pyrene using a copper(I)-catalyzed oxidative homocoupling reaction

Investigating the impact of integrated care models involving pharmacists, nurses, and laboratories on healthcare quality and efficiency

Background: The inclusion of healthcare professionals, such as pharmacists, nurses, and labs, in patient care has received more attention recently since it has the potential to enhance the quality and effectiveness of healthcare. Nonetheless, it is important to conduct a thorough examination of the current research in order to ascertain the effects of integrated care models that include these professions. Aim: This study seeks to examine the effects of integrated care models that include pharmacists, nurses, and labs on the quality and efficiency of healthcare. More precisely, the evaluation aims to combine current research about patient outcomes, cost reductions, and healthcare use in these models. Furthermore, the study seeks to analyze the distinct responsibilities and contributions of pharmacists, nurses, and labs in the context of integrated care. Method: A methodical search technique was used to locate relevant studies in electronic databases, such as PubMed, MEDLINE, and Cochrane Library. The inclusion criteria were centered on studies that documented the effects of integrated care models, which included the involvement of pharmacists, nurses, and labs, on the quality and efficiency of healthcare. Both quantitative and qualitative research were taken into account for inclusion