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In this study, new 4-chloro-5-(2-isopropyl-5-methylphenoxy)phthalonitrile compound, containing bioactive thymoxy group, and its metal-free phthalocyanine and metallo-phthalocyanine derivatives were synthesized for the first time. Their structures were determined by spectroscopic methods such as FTIR, UV–Vis, 1H-, and 13C-NMR (for phthalonitrile derivative), MALDI-TOF mass spectrometry (for phthalocyanine derivatives) and elemental analysis as well. The phthalocyanines showed excellent solubility in polar and nonpolar solvents without aggregation and absorb at long wavelengths with their high molar coefficient. In N,N-dimethylformamide, the effects of the type of central metal ions [metal-free, indium(III) acetate, lutetium(III) acetate, magnesium(II) or zinc(II)] in the phthalocyanine, containing bioactive thymoxy group, cavity on the spectroscopic, photophysical, and photochemical properties of the phthalocyanines were determined. These features are compared with each other. Lutetium(III) acetate phthalocyanine did not show any fluorescence, while metal-free phthalocyanine and indium(III) acetate phthalocyanine showed low fluorescence. It was determined that magnesium phthalocyanine significantly enriched the fluorescence, and zinc phthalocyanine had appropriate and sufficient fluorescence. Lutetium(III) acetate and zinc(II), especially indium(III) acetate phthalocyanines, could produce large amounts of singlet oxygen. Metal-free and magnesium phthalocyanines had the capacity to produce sufficient singlet oxygen (it means production of enough amount of singlet oxygen by a photosensitizer candidate during PDT applications). All phthalocyanines have sufficient and suitable photostability (it means an ideal photosensitizer should be stable under light irradiation until complete its PDT activation, and it should be decomposed after its PDT activation so that it does not accumulate in the body). With these determined properties, magnesium(II), especially indium(III) acetate and zinc(II) phthalocyanines, may be suitable candidates as type II photosensitizers for photodynamic therapy applications. Lutetium(III) acetate phthalocyanine may be a photosensitizer candidate in photocatalytic applications.

In this study, the effects of electron-withdrawing or electron-releasing groups in methyl benzoate esters, which are widely used in the fragrance industry, on the antioxidant and antibacterial activities of the compounds were investigated. Firstly, methyl benzoates with electron-withdrawing (NO2 and Cl groups) or electron-donating groups (CH3 and OCH3 groups) in the para position, which are commercial compounds, were synthesized, and extensively studied in terms of reaction conditions, and spectral data in their instrumental analysis methods. Then, the synthesized compounds were evaluated for their antioxidant, antibacterial, and cytotoxic activities. Among them, methyl 4-nitrobenzoate exhibited the highest inhibition against Staphylococcus aureus and Pseudomonas aeruginosa. Methyl 4-methoxybenzoate was selected for cytotoxicity evaluation due to its high antioxidant activity, and while the results indicated a dose-dependent decrease in cell viability, lower concentrations may still be considered for cosmetic applications. These findings suggest that antioxidant activity and cytotoxic activity are directly related to the electron density of the molecule. Therefore, this very up-to-date research covers many implications for organic chemistry, medicinal chemistry, biotechnology, and microbiology. Therefore, the results obtained may have great potential to be applied in the cosmetic industry and could be used as exceptionally useful information on alternative raw material selection for researchers in the fragrance industry. These results also suggest that methyl benzoates have potential as lead compounds for the development of novel antioxidant, antibacterial, and cytotoxic agents, but further studies are needed to fully explore their applications in various fields.

Electrochemical properties of MPcs were determined with electrochemical and in-situ spectroelectrochemical measurements to investigate the influence of the metal center and the number and positions of the substituents. While H2Pc only illustrated Pc based redox processes, the incorporation of TiO2+ and Cl−1-Mn3+ cations into the cavity of Pc ring considerably altered the redox richness of the complexes. Two metal-based reduction couples were observed in addition to the Pc-based processes for both of TiOPc and MnPc. Moreover, altering the number and position of 4-(2-phenylpropan-2-yl)phenoxy substituents slightly influenced the basic redox activity of Pc ring and metal centers. All of these results supported the proposed structure of the complexes. During the redox reactions, pronounced spectral changes were observed with the in situ spectroelectrochemical measurements which caused distinct color changes. Rich redox responses and pronounced spectral and color changes of the complexes indicated their worth as functional material in various electrochemical technologies.

A new series of 4-methyl-2-{2-[(aryl)methylidene]hydrazinyl}-1,3-thiazole (2a-i), N-(4-acetyl-5-aryl)4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamides (3a-b) and N-(5-(4-(substituted phenyl)-1,3,4-thiadiazol-2-yl)acetamides (3c-i) were synthesized by the reaction of 2-((aryl)methylene)hydrazine-1-carbothioamides (1a-i) and acetic anhydride or chloroacetone. The cytotoxic activities of the products were evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay against Hela cervical cancer, MCF-7 breast carcinoma and HT-29 colorectal cancer cell lines. Thiazole based compounds 2a, 2b, 2f and 2i, bearing 4-bromothiophen-2-yl, naphthalen-2-yl, 2,5-difluorophenyl and 4-(trifluoromethoxy)phenyl moieties, respectively; also N-(4-acetyl-5-(naphthalen-2-yl)-4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamide (3b) and N-(5-(2,6-difluorophenyl)-1,3,4-thiadiazol-2-yl)acetamide (3d) exhibited significant anticancer activity against three cancer cell lines. Moreover, these active compounds were further evaluated by apoptotic protein levels. The results showed that these thiazole and thiadiazole compounds induced apoptosis of cancer cells.

Today, usage of NSAIDs (nonsteroidal anti-inflammatory drugs) is very common. However, it has been proven by many studies that NSAIDs with free carboxylic acid group damage the GI (gastrointestinal) system. Our aim was to mask the acidic groups of NSAIDs to prevent or reduce their side effects while preserving their pharmacological effects. In this study, new amide derivatives of known NSAIDs, compounds 11–20, were synthesized to investigate their analgesic and anti-inflammatory effects using in vivo models. While compound 11 showed the most remarkable anti-inflammatory activity by 60.9% inhibition value at 200 mg/kg dose, compounds 11, 12, 15 and 18 had almost the same analgesic activity to that of acetylsalicylic acid (100 mg/kg) and flurbiprofen (100 mg/kg). In addition, all test compounds used at high dose (200 mg/kg, p.o) did not show any acute toxicity. COX-1 and COX-2 inhibition properties of all compounds were measured by biochemical methods and the interaction of the most active compounds with COX enzymes is elucidated by computer-assisted virtual screening methods. It was determined by in vitro enzyme inhibition studies that compound 11 and 13, synthesized from selective COX-1 inhibitors dexketoprofen and flurbiprofen, are selective COX-2 inhibitors. Moreover, compounds 11–13 were found to be non-mutagenic according to the mutagenicity assay using Salmonella TA98 and TA100 strains with and without metabolic activation. Finally, the prediction of ADMET profile and drug-likeness properties of compounds 11–20 were examined and the obtained results were evaluated.

Bu çalışmada, 2,4-bis-(3-metoksitolil)-1,3-ditiya-2,4-difosfetan 2,4-disülfür ([((CH3)C6H3(OCH3)-P(S)S)2]) bileşiği yeniden sentezlendi. Bu bileşiğin alkollerle reaksiyonundan literatürde bilinen iki ditiyofosfonik asiti ([HS2P(R’)(ORn)], HLn; R’=(CH3)C6H3(OCH3); R1= Etil-, L1, R2= 2-propil-, L2) sentezlendi. Ham ditiyofosfonik asitler kuru amonyak gazıyla ligandlarına ([NH4][S2P(R’)(ORn)]) dönüştürüldü. Etil alkol ortamında bu ligandların kadmiyum tuzlarıyla reaksiyonlarından çift çekirdekli yeni ditiyofosfonato Cd(II) kompleksleri sentezlendi ([Cd(μ-Ln)2(Ln)2]). Komplekslerin yapıları; elementel analizi, kütle spektrometresi (ESI), FT-IR, Raman, NMR (1H, 13C, 31P) spektroskopisiyle aydınlatıldı. In this study, 2,4-bis(3-methoxytolyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide which is formulated as [((CH3)C6H3(OCH3)-P(S)S)2] compound was resynthesized. From this, two dithiophosphonic acids which were previously known were synthesized from the reaction of this compound with alcohols ([HS2P(R’)(ORn)], HLn; R’=(CH3)C6H3(OCH3); R1= Ethyl-, L1; R2= 2-propyl-, L2). These acids were converted to corresponding ammonium salts, ([NH4][Ln]). The ammonium salts were further reacted with CdCl2.H2O to prepare dinuclear three new dithiophosphonato cadmium(II) complexes, ([Cd(μ-Ln)2(Ln)2]) in ethanol medium. Structures of the complexes were characterized by elemental analysis, mass spectrometry (ESI), FT-IR, Raman, NMR (1H, 13C, 31P) spectroscopy.

Perthiophosphonic acid anhydrides (PTPA) are used as a starting agent in the synthesis of phosphorus-sulfur compounds[1].These derivatives can be classified into dithiophosphates, dithiophosphinates and dithiophosphonates (DTPOA). In this survey, we synthesized new DTPOAs starting from PTPAs formerly synthesized by us ADDIN EN.CITE Bulat202232[32]323217Bulat, ElifSağlam, Ertuğrul GaziZeyrek, Celal TuğrulAkkoç, SenemZorlu, YunusDal, HakanNi(II) complexes with 1,3,2,4-dithiadiphosphetane 2,4-disulfide-based ligands: Structural insights, theoretical studies, and anticancer activitiesApplied Organometallic ChemistryApplied Organometallic Chemistrye6821361020220268-2605https://onlinelibrary.wiley.com/doi/abs/10.1002/aoc.6821https://doi.org/10.1002/aoc.6821[2,3]. In other words, new dithiophosphonic acids (HS2P((2,4-CH3O)2-C6H3)(ORn), HLx,y; RX1=n-propyl-, RX2=2-butyl-,Ry=methyl- were synthesized by reacting of 2,4-bis(3,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide, (SAV-A1) and 2,4-bis(2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide, (SAV-A2) with aliphatic alcohols. All DTPOAs were transformed to relating to ammonium salts, [NH4Lx,y] (Scheme 1).

© 2022 Elsevier B.V.Novel CoPc, CuPc, Fe(OAc)Pc and Mn(Cl)Pc were synthesized by using original 4-chloro-5-(2-isopropyl-5-methylphenoxy)phthalonitrile in order to investigate their potential redox applications suitable with their chemical and physical characteristics. The molecular structures of new compounds were determined with spectroscopic methods such as elemental analysis, FT-IR, UV–vis, NMR and MALDI TOF MS. Redox behaviours of Fe(OAc)Pc and Mn(Cl)Pc complexes have been probed by using diverse voltammetric techniques such as cyclic (CV) and square wave voltammetry (SWV). In addition, the colour alterations accompanying spectral changes were perused concurrently with electrocolorimetric measurements, and electrocatalytic efficiencies of the all compounds were perused in oxygen reduction reaction.

A novel radiolabelling method exploiting 11C-dithiocarbamate ligands has been used to generate 11C-labelled Au(I), Au(III), Pd(II) and Pt(II) complexes in high radiochemical yields (71–99%). Labelled complexes were prepared in a rapid one-pot procedure via the substitution reaction of 11C-dithiocarbamate ligands with appropriate transition metal chloride precursors.

Thiazolyl-hydrazones (THs) exhibit a wide spectrum of biological activity that can be enhanced by complexation with various metal ions. Zn(II) complexes with α-pyridine-1, 3-TH ligands may represent an alternative to the standard platinum- based chemotherapeutics. In addition, they show photoluminescence properties and thus can be regarded as multifunctional materials. In this study, we synthesized and characterized three neutral Zn(II) complexes (1–3) with pyridine-based TH ligands HLS1‒3 in order to investigate the influence of the ligands charge on the structure and intermolecular interactions in the solid state, and consequently photophysical properties. The deprotonation of the ligands mainly affects the relative energies of electronic levels in the complexes, compared to cationic counterparts, resulting in similar photoluminescence mechanisms and quantum yields with a small shift in emission energy. The influence of the substitution at the ligands’ periphery on the selected quantum molecular descriptors of the complexes is localized to the substitution site. Also, the substituents did not considerably influence the redox responses of the complexes. However, predominant spectral changes were observed in the course of the first reduction and oxidation processes which caused distinct spectral color changes indicating their possible functionality for electrochromic applications. In addition, complex 1 showed antiproliferative activity with GI50 values below 2 µM on all tested cancer cell lines.

Background The molecular chaperone, Hsp90, is a key player in the protein quality control system that maintains homeostasis under cellular stress conditions. It is a homodimer with ATP-dependent activity, and is a prominent member of the chaperone machinery that stabilizes, matures and (re)folds an extensive list of client proteins. Hsp90 occurs as four isoforms, cytosolic Hsp90α and Hsp90β, mitochondrial TRAP1 and Grp94 present in the endoplasmic reticulum. An aberrant role of Hsp90 has been attributed to several cancers and neurodegenerative disorders. Consequently, Hsp90 has emerged as an attractive therapeutic target. However, pan-Hsp90 inhibition often leads to detrimental dose-limiting toxicities. Novel strategies for Hsp90-targeted therapy intend to avoid this by using isoform-specific Hsp90 inhibition. In this respect, the radiosynthesis of carbon-11 labeled SNX-ab was developed and [11C]SNX-ab was evaluated as a Hsp90α,β isoform-selective PET probe, which could potentially allow to quantify in vivo Hsp90α,β expression. Results [11C]SNX-ab was synthesized with excellent radiochemical yields of 45% and high radiochemical purity (> 98%). In vitro autoradiography studies on tissue slices of healthy mouse brain, mouse B16.F10 melanoma and U87 glioblastoma using homologous (SNX-ab, SNX-0723) and heterologous (Onalespib and PU-H71) Hsp90 inhibitors demonstrated only limited reduction of tracer binding, indicating that the binding of [11C]SNX-ab was not fully Hsp90-specific. Similarly, [11C]SNX-ab binding to U87 cells was not efficiently inhibited by Hsp90 inhibitors. Ex vivo biodistribution studies in healthy mice revealed limited brain exposure of [11C]SNX-ab and predominantly hepatobiliary clearance, which was confirmed by in vivo full-body dynamic µPET studies. Conclusion Our results suggest that [11C]SNX-ab is not an ideal probe for in vivo visualization and quantification of Hsp90α/β expression levels in tumour and brain. Future research in the development of next-generation Hsp90 isoform-selective PET tracers is warranted to dissect the role played by each isoform towards disease pathology and support the development of subtype-specific Hsp90 therapeutics.

A series of UiO-66 materials with different functional groups (−H, −NH2, and −NO2) have been evaluated for the adsorption and release of a common ocular drug such as brimonidine tartrate. UiO-66 samples were synthesized under solvothermal conditions and activated by solvent exchange with ethanol. Experimental results suggest that the incorporation of surface functionalities gives rise to the development of structural defects (missing linker defects) but without altering the basic topology of the UiO-66 framework. These defects improve the adsorption performance of the parent metal–organic framework (MOF), while the bulkier functionalities infer slower release kinetics, with the associated benefits for prolonged delivery of brimonidine. Among the evaluated MOFs, defective UiO-66-NO2 can be proposed as the most promising candidate due to the combination of a larger brimonidine volumetric uptake (680 mg/cm3), a prolonged delivery (period of up to 25 days), a small particle size, and a larger instability. Contrariwise, at high concentrations UiO-66-NO2 has higher toxicity toward human retinal pigment epithelium cells (ARPE-19) compared to the pure and NH2-functionalized UiO-66. Authors would like to acknowledge financial support from the Ministerio de Ciencia e Innovación (Project PID2019-108453GB-C21), H2020 (Project MSCA-RISE-2016/NanoMed) and Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital (Project CIPROM/2021/022).

New 2,4- bis (2,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide, (SAV-A2), was synthesized from the reaction P 4 S 10 and 1,3-dimethoxybenzene. SAV-A2 was reacted with alcohols to form dithiophos- phonic acid monoesters (HLn, HS 2 P((2,4-CH 3 O) 2 C 6 H 3 )(ORn); n = 1–3, R1 = 2–butyl–; R2 = n -pentyl-; R3 = 4–tert –but-benzyl-). The acids were converted to the ammonium salts ([NH 4 L n ]) to serve as the source of the ligands (Ln), to obtain Ni(II) complexes, ([N i (L n ) 2 ]). [Ni(L2) 2 ] crystal structure was elucidated by single-crystal X-ray diffraction analysis. In addition, Density Functional Theory (DFT) calculations of [Ni(L2) 2 ] was performed. The molecular docking studies of the complex with liver cancer protein, PDB ID: 3WZE and colon cancer antigen proteins, ID 2HQ6 were done compare with experimental and the- oretical results. All compounds were tested on liver- and colon cancer cell lines. Among the complexes tested, [Ni(L3) 2 ] showed an activity closer to that of cisplatin against the colon cancer cell line. The other compounds were found to be have less active.

The first synthesis of 2,4-bis(3,4-dimethoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide (SAV-A1 reagent) was achieved. Seven oxo-alkyl esters (HLn) were synthesized thereof. Ni(II) complexes ([Ni(Ln)(2)]) of these ligands were prepared in ethanol. The structures were identified by spectral studies. Ni(II) complexes were unambiguously determined by X-ray crystallography. In addition, the ligands and their Ni(II) complexes were tested on two different human cancer cell lines, including liver and colon. Moreover, density functional theory (DFT) calculations of the Ni(II) complexes were performed, and the molecular docking studies of these compounds with liver cancer protein, PDB ID: 3WZE and colon cancer antigen proteins, ID 2HQ6 were presented to investigate and predict potential interactions.

The effect of solvent has been investigated for the synthesis of bismuth gallate compounds, of which the water-based bismuth subgallate has been used as an active pharmaceutical ingredient (API) for over a century. Using methanol as a solvent, two new bismuth gallates were acquired: first a flexible 3-periodic metal-organic framework (MOF) forms, which transforms upon extended synthesis times into a layered 2-periodic coordination polymer of the same bismuth-to-gallate ratio. The structures were determined by three-dimensional electron diffraction. Synthesis in ethanol resulted in the formation of the MOF phase, but not the layered phase. The layered material of the methanol-based synthesis was used as a Lewis acid catalyst due to its higher stability, showing a comparatively quick and regiospecific conversion of styrene oxide to 2-methoxy-2-phenylethanol, indicating the presence of open metal sites in the material. The acquisition of bismuth gallate structures of varying periodicity highlights the prospect of acquiring novel MOFs and coordination polymers from the same components of APIs. ispartof: DALTON TRANSACTIONS vol:51 issue:37 pages:14221-14227 ispartof: location:England status: published

The novel and highly soluble cobalt(II), copper(II) and manganese(III) phthalocyanines ((Pc-Co, Pc-Cu, and Pc-Mn) bearing 3-(5-(3,5-dimethoxyphenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)phenol have been synthesized and characterized by FT-IR, NMR, UV-Vis and mass spectroscopic methods. Additionally, electrochemical and spectroelectrochemical properties of these phthalocyanine compounds were investigated. Due to the redox inactivity of the Cu2+ central cation of (Pc-Cu), Pc based reductions and oxidation processes are recorded. [(CoPc2-)-Pc-II]/[(CoPc2-)-Pc-I](1-) and [(CoPc2-)-Pc-II]/[(CoPc2-)-Pc-III](1+) couples for the central metal redox reactions, and [(CoPc2-)-Pc-I](1-)/[(CoPc3-)-Pc-I](2-), [(CoPc3-)-Pc-I](2-)/[(CoPc4-)-Pc-I](3-) and [(CoPc2-)-Pc-III](1+)/[(CoPc1-)-Pc-III](2+) couples for the Pc based reduction and oxidation are observed respectively with (Pc-Co). Like (Pc-Co), (Pc-Mn) also illustrated metal-based reduction processes, [Cl1--(MnPc2-)-Pc-III]/[Cl1--(MnPc2-)-Pc-II](1-) and [Cl1--(MnPc2-)-Pc-II](1-)/[Cl1--(MnPc2-)-Pc-I](2-) in addition to the Pc based [Cl1--(MnPc2-)-Pc-I](2-)/[Cl1--(MnPc3-)-Pc-I](3-), [Cl1--(MnPc3-)-Pc-I](3-) /[Cl1--(MnPc4-)-Pc-I](4-) and [Cl1--(MnPc2-)-Pc-III]/[Cl1--(MnPc1-)-Pc-III](1+) redox couples were also recorded. These redox mechanisms were supported with the characteristic spectral changes observed during the in-situ spectroelectrochemical measurements. Especially metal-based electron transfer changes caused distinct spectral and color changes, which are the desired properties of the complexes for the possible opto-electrochemical applications. (C) 2022 Elsevier B.V. All rights reserved.

In this study, perthiophosphonic acid anhydrides which are previously synthesized (2,4-bis(3-methoxytolyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide ([((3-methoxytolyl)P(S)S)2], SAV-B1 reagent and 2,4-bis(ferrocenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide [((ferrocenyl)P(S)S)2], FcLR, Ferrocenyl Lawesson's Reagent) react with alcohols to obtain new dithiophosphonic acids (3-methoxytolyl=(CH3)(OCH3)C6H3- and Xn=Alkyl group (R) for SAV-B1, HXn; R1=3-pentyl-, HX1; R2=2-butyl-, HX2; R3=2-pentyl-, HX3 and Fc=Ferrocenyl- and Yn=Alkyl or aryl group (R') for FcLR, HYn; R'1=4-tert-cyclohexyl-, HY1; R'2=2-phenyl-1-propyl-, HY2). These products were later transformed into their ammonium salts ([NH4][Xn], [NH4][Yn]). The structures of ammonium salts were characterized by mass, FT-IR, 1H-, 13C- and 31P-NMR spectroscopy and elemental analysis.

© 2022 Indian Chemical SocietyThe main aim of this study is to formulate the combination of the bioactive composite containing chitosan/β -tricalcium phosphate (CH/β-TCP) as potential drug delivery platforms for the sustained release of antibiotics. Herein the mode of amoxicillin (AMX) maintained in the β-TCP/chitosan composite was characterized using XRD, FT-IR to confirm the phase purity and functional groups. SEM was used to examine the size and shape of particles. The SEM images of the biocomposites after drug release confirmed that they are biodegradable. In vitro drug release experiments in PBS (pH 7.4) revealed a sustained release profile in a neutral medium. Drug release profiles were evaluated according to five different kinetic models including Zero Order, First Order, Higuchi, Hixon Crowel, and Korsmeyer-Peppas. The release profile was best expressed by the Korsmeyer Peppas model because the results showed high linearity. Overall, the positive effect of chitosan coating on the drug elution profile of β-TCP as carriers for the controlled delivery of antibiotics was regarded as biocompatible for the controlled drug delivery system.

© 2023 Elsevier B.V.Four new isatin bisthiocarbohydrazone ligands (H2L1, H2L2, H2L3, H2L4) were synthesized by the condensation of salicylaldehyde, 5-bromosalicylaldehyde, 5-chlorosalicylaldehyde and 5-nitrosalicylaldehyde with isatin monothiocarbohydrazone, respectively. The mixed ligand Ni(II) complexes {[NiL1(P)], [NiL2(P)], [NiL3(P)] and [NiL4(P)]} containing triphenylphosphine (P: triphenylphosphine, PPh3) of these bisthiocarbohydrazone ligands were synthesized. The synthesized compounds were characterized by elemental analysis, FT-IR, 1H NMR, UV–Vis spectroscopy techniques and conductivity measurements. In the complexes, the bisthiocarbohydrazone ligands coordinate to nickel through ONS mode. The complexes are diamagnetic and exhibit square planar geometry. The crystal structures of two ligands, H2L1 and H2L3, and two complexes, [NiL1(P)] and [Ni3(L3)2(P)2], whose single crystals were obtained, were determined by single crystal X-ray diffraction technique. The crystal structure of [NiL1(P)] complex is monomeric and compatible with the structure of the solid complex. A new trinuclear Ni(II) complex, [Ni3(L3)2(P)2], was obtained by the crystallization of monomeric solid [NiL3(P)] complex in a different solvent mixture. Redox properties of bisthiocarbohydrazone ligands (H2L1-H2L4) bearing S1 or S2 substituents and their nickel(II) complexes {[NiL1(P)]-[NiL4(P)]} were investigated with cyclic voltammetry and in situ spectroelectrochemistry. Voltammetric analyses indicated that all ligands exhibited four quasi-reversible reduction and one irreversible oxidation process. Complexation of the ligands with Ni(II) cation decreased the number of the reduction processes and caused these processes to have more negative potentials. Significant spectral changes were also observed in the in situ spectroelectrochemical analysis due to electron transfer reactions. In addition, electrochemical responses of monosubstituted salicylaldehyde derivative isatin bisthiocarbohydrazone ligands and their nickel(II) complexes were compared with their disubstituted derivatives.

The pathogenic variant E92K (c.274G > A) of the CFTR gene is rare in America and Europe, but it is common for people with cystic fibrosis from Russia and Turkey. We studied the effect of the E92K genetic variant on the CFTR function. The function of the CFTR channel was studied using the intestinal current measurements (ICM) method. The effects of CFTR modulators on the restoration of the CFTR function were studied in the model of intestinal organoids. To assess the effect of E92K on pre-mRNA splicing, the RT-PCR products obtained from patients’ intestinal organoid cultures were analyzed. Patients with the genetic variant E92K are characterized by an older age of diagnosis compared to homozygotes F508del and a high frequency of pancreatic sufficiency. The results of the sweat test and the ICM method showed partial preservation of the function of the CFTR channel. Functional analysis of CFTR gene expression revealed a weak effect of the E92K variant on mRNA-CFTR splicing. Lumacaftor (VX-809) has been shown to restore CFTR function in an intestinal organoid model, which allows us to consider the E92K variant as a promising target for therapy with CFTR correctors.

© 2022This work involves the synthesis and characterization of metallic (Co, Fe, Mn, Ni, Zn) ball-type phthalocyanine precursors by using novel 4,4′-(((4-(tert-butyl)-1,2-phenylene)bis-(methylene))bis(oxy))diphthalonitrile starting compound. The classical oxo-bridge in phthalocyanines was altered with the -OCH2- bridge first time for these ball-type phthalocyanine precursors, and the effects of this change on the chemical, physical and spectral features of phthalocyanine complexes were investigated, in the study. The redox properties of phthalocyanines were researched by electrochemical and in situ spectroelectrochemical measurements on a Pt working electrode in non-aqueous medium. The color changes involved in the redox processes were observed via in situ electrocolorimetric techniques. Electrochemical and UV–Vis spectral measurements exhibited that the compounds had reversible and serial one-electron reduction and oxidation processes. Furthermore, they also had nitrile reduction processes because of opened nitrile groups located at peripheral tails of the phthalocyanine complexes. The plentiful redox conducts of the complexes such as Pc ring based and/or central redox active metal-based reduction and oxidation reactions at low potentials showed that these complexes can be used as functional materials. Because of the apparent spectral and net color changes, the complexes are suitable for utilization in electrochromic devices. Moreover, their rich redox features are a sign of their high electrocatalytic activity for oxygen reduction.

The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will likely inform the design of next-generation catalysts based on aluminium metalloligands.

Background The development of radiopharmaceuticals requires extensive evaluation before they can be applied in a diagnostic or therapeutic setting in Nuclear Medicine. Chemical, radiochemical, and pharmaceutical parameters must be established and verified to ensure the quality of these novel products. Main body To provide supportive evidence for the expected human in vivo behaviour, particularly related to safety and efficacy, additional tests, often referred to as “non-clinical” or “preclinical” are mandatory. This document is an outcome of a Technical Meeting of the International Atomic Energy Agency. It summarises the considerations necessary for non-clinical studies to accommodate the regulatory requirements for clinical translation of radiopharmaceuticals. These considerations include non-clinical pharmacology, radiation exposure and effects, toxicological studies, pharmacokinetic modelling, and imaging studies. Additionally, standardisation of different specific clinical applications is discussed. Conclusion This document is intended as a guide for radiopharmaceutical scientists, Nuclear Medicine specialists, and regulatory professionals to bring innovative diagnostic and therapeutic radiopharmaceuticals into the clinical evaluation process in a safe and effective way.

Methodological bias can directly affect the interpretation of research data. Studies reporting on excavated skeletons represent a valuable source of information in medicine, dentistry, archaeology and anthropology, and forensic sciences. However, these studies represent a specific setting with their own methodology, for which no quality assessment tool is available. The aim was to develop a critical appraisal tool to assess the methodological quality of studies reporting on archaeologically excavated human skeletons. An international Delphi study was therefore conducted to support item generation and ensure content validity for a new tool. Experts from the following domains were consulted: dentistry, forensic sciences, archaeology and anthropology, general medicine, epidemiology, and statistics. Participants judged the relevance and comprehensiveness of items retrieved from the literature. Consensus was predefined as 75% agreement between experts, and achieved within two Delphi rounds. As a result, 44 and 32 participants completed the first and second Delphi rounds, respectively, achieving consensus on 17 items. This research provides the first evidence-based tool for the methodological assessment of studies reporting on archaeologically excavated skeletons. Clinicians and researchers can use this tool for critical appraisal of studies or when performing systematic reviews. Future research will focus on psychometric testing of the newly developed tool. ispartof: Archaeometry vol:64 issue:6 pages:1499-1513 status: Published online

The incorporation of transition metals (TMs) such as Co, Fe, and Mn into SnO2 substantially improves the reversibility of the conversion and the alloying reaction when used as a negative electrode active material in lithium-ion batteries. Moreover, it was shown that the specific benefits of different TM dopants can be combined when introducing more than one dopant into the SnO2 lattice. Herein, a careful characterization of Co and Mn co-doped SnO2 via transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction including Rietveld refinement is reported. Based on this in-depth investigation of the crystal structure and the distribution of the two TM dopants within the lattice, an ex situ X-ray photoelectron spectroscopy and ex situ X-ray absorption spectroscopy were performed to better understand the de-/lithiation mechanism and the synergistic impact of the Co and Mn co-doping. The results specifically suggest that the antithetical redox behaviour of the two dopants might play a decisive role for the enhanced reversibility of the de-/lithiation reaction.

The recycling of minor actinides from dissolved nuclear fuels by hydrometallurgical separation is one challenging strategy for the management of spent fuel. These future separation processes will likely be based on solvent extraction processes in which an organic solvent system (extractant and diluent) will be contacted with highly radioactive aqueous solutions. To establish a separation between different elements in spent nuclear fuel, many extractants have been studied in the past. A particular example is N,N,N′,N′-tetraoctyl diglycolamide (TODGA), which co-extracts lanthanides and actinides from nitric acid solutions into an organic phase (e.g. TODGA in n-dodecane). The radiolytic stability of these extractants is crucial, since they will absorb high doses of ionizing radiation during their usage. Worldwide, different gamma irradiation facilities are employed to expose extractants to ionizing radiation and gain insight in their radiation stability. The facilities differ in many ways, such as their environment (pool-type or dry), configuration and gamma sources (often 60Co or spent nuclear fuel). In this paper, a dosimetric assessment is made using different dosimeter systems in a pool-type irradiation facility, which has the advantage to be flexible in its arrangement of 60Co sources. It is shown that Red Perspex dosimeters can be used to accurately characterize this high dose rate gamma irradiation field (approx. 13.6 kGy h−1), after comparison with alanine, Fricke and ceric-cerous dosimetry in a lower dose rate gamma irradiation field (approx. 0.5 kGy h−1). A final validation of the whole chain of techniques is obtained by reproduction of the dose constants for TODGA in n-dodecane.

The formation of a thin layer, the so-called Joint Oxyde-Gaine (JOG), between the (U,Pu)O2 fuel pellets and the cladding has been observed in fast neutron reactors, due to the accumulation of volatile fission products. Cs2MoO4 is known to be one of the major components of the JOG, but other elements are also present, in particular tellurium and palladium. In this work, an investigation of the structural and thermodynamic properties of Cs2TeO4 and Cs2Mo1–xTexO4 solid solution is reported. The existence of a complete solubility between Cs2MoO4 and Cs2TeO4 is demonstrated, combining X-ray diffraction (XRD), neutron diffraction (ND), and X-ray absorption spectroscopy (XAS) results. High-temperature XRD measurements were moreover performed on Cs2TeO4, which revealed the existence of a α–β phase transition around 712 K. Thermal expansion coefficients were also obtained from these data. Finally, phase equilibra points in the Cs2MoO4–Cs2TeO4 pseudobinary phase diagram were collected using differential scanning calorimetry and used to develop a thermodynamic model for this system using a regular solution formalism., The existence of a complete solid solution between Cs2MoO4 and Cs2TeO4 is demonstrated combining XRD, ND, and EXAFS data. The hexavalent states of Mo and Te in the Cs2Mo1−xTexO4 solid solution have been confirmed by XANES. The existence of a phase transition at (712 ± 5 K) in Cs2TeO4 (from an orthorhomic to an hexagonal structure) is revealed. Phase equilibria measurements in the Cs2MoO4−Cs2TeO4 phase diagram are reported, and a regular solution model has been developed.

A new method for interpreting lead isotope ratios of artefacts is presented: a numerical and graphical 'match-no match' with possible raw materials. By calculating the definite integral under the kernel density estimate plot of different mining districts, using open-access software and legacy data, the relative probability that an object is made of an ore is indicated. A match with the reference data set may indicate the true origin, while no match indicates an unknown origin, that is, not present in the data set of mineral resources. Likewise, the composite or recycled nature of artefacts can be investigated in a probabilistic manner.

Aβ4–42 is the major subspecies of Aβ peptides characterized by avid Cu(II) binding via the ATCUN/NTS motif. It is thought to be produced in vivo proteolytically by neprilysin, but in vitro experiments in the presence of Cu(II) ions indicated preferable formation of C-terminally truncated ATCUN/NTS species including CuIIAβ4–16, CuIIAβ4–9, and also CuIIAβ12–16, all with nearly femtomolar affinities at neutral pH. Such small complexes may serve as shuttles for copper clearance from extracellular brain spaces, on condition they could survive intracellular conditions upon crossing biological barriers. In order to ascertain such possibility, we studied the reactions of CuIIAβ4–16, CuIIAβ4–9, CuIIAβ12–16, and CuIIAβ1–16 with reduced glutathione (GSH) under aerobic and anaerobic conditions using absorption spectroscopy and mass spectrometry. We found CuIIAβ4–16 and CuIIAβ4–9 to be strongly resistant to reduction and concomitant formation of Cu(I)–GSH complexes, with reaction times ∼10 h, while CuIIAβ12–16 was reduced within minutes and CuIIAβ1–16 within seconds of incubation. Upon GSH exhaustion by molecular oxygen, the CuIIAβ complexes were reformed with no concomitant oxidative damage to peptides. These finding reinforce the concept of Aβ4–x peptides as physiological trafficking partners of brain copper., Aβ4−16, Aβ4−9, and Aβ12−16, oligopeptide products of β-amyloid degradation by neprilysin, bind CuII ions very tightly and are considered as possible CuII carriers in the brain. We demonstrated that CuII(Aβ4−x) complexes, but not CuII(Aβ12−16), are kinetically resistant to reduction by glutathione. No covalent Aβ peptide modifications were observed during the copper reduction and reoxidation by ambient oxygen, yielding the original complexes. These features suggest that CuII(Aβ4−x) complexes might be able to cross the blood−brain barrier.

Titanium(IV) complexes of amino-tris(phenolate) ligands (LTiX, X = chloride, isopropoxide) together with bis(triphenylphosphine)iminium chloride (PPNCl) are active catalyst systems for the ring-opening copolymerization of carbon dioxide and cyclohexene oxide. They show moderate activity, with turnover frequency values of ∼60 h–1(0.02 mol % of catalyst, 80 °C, 40 bar of CO2) and high selectivity (carbonate linkages >90%), but their absolute performances are lower than those of the most active Ti(IV) catalyst systems. The reactions proceed with linear evolution of polycarbonate (PCHC) molar mass with epoxide conversion, consistent with controlled polymerizations, and evolve bimodal molar mass distributions of PCHC (up toMn= 42 kg mol–1). The stoichiometric reaction between [LTiOiPr] and tetraphenylphosphonium chloride, PPh4Cl, allows isolation of the putative catalytic intermediate [LTi(OiPr)Cl]−, which is characterized using single-crystal X-ray diffraction techniques. The anionic titanium complex [LTi(OR)Cl]−is proposed as a model for the propagating alkoxide intermediates in the catalytic cycle.

Cloisonne-style motifs are rare and enigmatic in Chinese painted enamels because of their distinct technological development at the end of the 18th century. Five late Qianlong to Jiaqing period (1736-1820) Chinese painted enamels with cloisonne-style motifs are investigated using environmental scanning electron microscopy-energy dispersive X-ray spectroscopy. Back-scattered electron images and elemental analysis are combined to study the decorative enamelled surface. The compositions of the layers within the enamel, that of the counter enamel and the polychrome decoration on the surface are determined and identified. Fluorine and elevated amounts of calcium were detected, indicating that fluorite was likely used as a raw material. The presence of this mineral, which is typical of Chinese cloisonne, confirms that these objects share both aesthetic and technological relationships.

Complexes [{Pt(C^C*)(μ-pz)}2] (HC^C*A = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene 1a, HC^C*B = 1-phenyl-3-methyl-1H-imidazol-2-ylidene 1b) react with methyl iodide (MeI) at room temperature in the dark to give compounds [{PtIV(C^C*)Me(μ-pz)}2(μ-I)]I (C^C*A2a, C^C*B2b). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded [Br(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Bn] (5a), which by heating in BnBr(l) became [{PtIV(C^C*A)Bn(μ-pz)}2(μ-Br)]Br (6a). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a SN2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as [(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)R]X (RX = MeI Int-Me, BnBr Int-Bn) and [(C^C*A)PtII(μ-pz)2PtIV(C^C*A)(R)X] (RX = MeI Int′-Me, BnBr Int′-Bn) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as [(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Me]BF4 (3a′) and used to get [I(C^C*A)PtIII(μ-pz)2PtIII(C^C*A)Me](4a), [(C^C*A)PtII(μ-pz)2PtIV(C^C*A)(Me)I](Int′-Me), and [{PtIV(C^C*)Me(μ-pz)}2(μ-I)]BF4 (2a′). The single-crystal X-ray structures of 2a, 2b, 3a′, and 5a along with the mono- and bi-dimensional 1H and 195Pt{1H} NMR spectra of all the named species allowed us to compare structural and spectroscopic data for high-valent complexes with the same core [{Pt(C^C*)(μ-pz)}2] but different oxidation states., This work was supported by the Spanish Ministerio de Economia y Competitividad (Ministerio de Ciencia Innovacion y Universidades)/FEDER (Project PGC2018-094749-B-I00), by the Gobierno de Aragon (Grupo E17_20R: Química Inorgánica y de los Compuestos Organometálicos) and by Internal Funds KU Leuven and FWO. L.A. acknowledges the support of a grant from the Gobierno de Aragón.

Three new complexes of Cu(II), Zn(II) and Cd(II) with bis(2-pyridyl)-di(4-methoxyphenyl)ethene (KT1), bis(µ2-chloro)-dichloro-bis(2-(2,2-di(4-methoxyphenyl)-1-(pyridin-2-yl)vinyl)pyridine)-di-copper(II) (CuKT1), dichloro-2-(2,2-di(4-methoxyphenyl)-1-(pyridin-2-yl)vinyl)pyridine-zinc(II) (ZnKT1) and hexakis(µ2-chloro)-dichloro-tetrakis(2-(2,2-di(4-methoxyphenyl)-1-(pyridin-2-yl)vinyl)pyridine)-tetra-cadmium(II) (CdKT1) were synthesized and characterized by IR spectroscopy, 1H NMR spectroscopy and single-crystal X-ray diffraction. The results reveal that ZnKT1 is a mononuclear complex, while CuKT1 and CdKT1 are binuclear and tetranuclear complexes, respectively. The central metal ions are surrounded by two N atoms of bis(2-pyridyl)-di(4-methoxyphenyl)ethene and Cl− ions including pendant and bridged ones. In the ZnKT1 complex, a distorted tetrahedral geometry is formed with Zn(II) as central ion and two chloride ions plus two nitrogen atoms of KT1 as surrounding atoms. CuKT1 is a binuclear complex with two square pyramids formed around the two Cu(II) ions. CdKT1 is a tetranuclear complex with two Cd(II) cations having coordination number six (distorted octahedral geometry) and the other two having coordination number five (distorted trigonal-bipyramidal geometry). The anticancer activity tests on four cancer cell lines, including KB, Hep-G2, Lu and MCF-7, show that ZnKT1 and CuKT1 are active against Hep-G2 and Lu but do not considerably damage KB and MCF-G7. CuKT1 has a considerable effect on two cancer cell lines, Hep-G2 and Lu, with IC50 values of 16(2) and 13(1) μM, respectively. CdKT1 exhibits excellent activity against all four cancer cell lines, with IC50 values ranging from 3.5(2) to 8.8(5) μM, which are lower than those of cisplatin. These complexes exhibit low cytotoxic activity on the normal cell line HEK-293A with IC50 values ranging from 10(1) to 74(5) µM.