Exploring the reductive CO fixation with amines and hydrosilanes using readily available Cu(II) NHC-phenolate catalyst precursors.

-Methylation of amines is of great interest in the synthesis of pharmaceuticals and valuable compounds, and the possibility to perform this reaction with an inexpensive and non-toxic substrate like CO and its derivatives is quite appealing. Herein, the synthesis of four novel homoleptic Cu(II) complexes with hybrid NHC-phenolate (NHC = -Heterocyclic Carbene) ligands is reported, and their use in the catalytic -methylation of amines with CO in the presence of hydrosilanes is explored. Both bidentate or tetradentate ligands can be used in the preparation of the complexes provided that the structural requirement that the two NHC and the two phenolate donors in the metal coordination sphere are mutually in is fulfilled.

Capturing Mercury-197m/g for Auger Electron Therapy and Cancer Theranostic with Sulfur-Containing Cyclen-Based Macrocycles.

The interest in mercury radioisotopes, Hg ( = 23.8 h) and Hg ( = 64.14 h), has recently been reignited by the dual diagnostic and therapeutic nature of their nuclear decays.

Synthesis and characterization of Pt(II) and Au(I) complexes with -oxy-heterocyclic carbene ligands (NOHCs).

Two -alkyloxy-'-phenylimidazolium proligands and the corresponding platinum(II) cyclometalated -alkyloxyimidazol-2-ylidene complexes with β-diketonate auxiliary ligands, [(C^C*)Pt(L∩L)] (L∩L = acetyacetonate (acac) or 1,3-bis(2,4,6-trimethylphenyl)-propane-1,3-dionato (mesacac)) were synthesized and fully characterized. In addition, a Au(I) monocarbene complex was synthesized, isolated and characterized. Solid-state structures of two cyclometalated platinum(II) NOHC complexes and the Au(I) NOHC complex were obtained providing structural proof.

Bis(N-Heterocyclic Carbene) Manganese(I) Complexes in Catalytic N-Formylation/N-Methylation of Amines Using Carbon Dioxide and Phenylsilane.

A series of six Mn(I) complexes with general formula [MnBr(bisNHC)(CO) ], having a bidentate bis(N-heterocyclic carbene) ligand (bisNHC), has been developed by varying the bridging group between the NHC donors, the nitrogen wingtip substituents and the heterocyclic ring. The synthesis of the complexes has been accomplished by in situ transmetalation of the bisNHC from the corresponding silver(I) complexes. Removal of the bromide anion affords the corresponding solvento complexes [Mn(bisNHC)(CO) (CH CN)](BF ).

Mechanochemical preparation of strongly emissive monosubstituted triarylphosphane gold(i) compounds activated by hydrogen bonding driven aggregations.

Gold(i) triarylphosphane compounds are a well-known class of coordination compounds displaying from mild to strong emissive properties. Mechanochemical approaches to the preparation, spectroscopic characterization, X-ray diffraction structural determination, and photophysical studies of green emissive neutral linear monophosphane or neutral pseudo-T-shaped or cationic bis-phosphane gold(i) compounds, are herein discussed. The mechanochemical approach to the preparation of gold(i) derivatives was particularly successful for ligands bearing the carboxylic group, while the preparation with esterified ligands yields better results with solvent-mediated methods.

Rapid Prototyping of 3D-Printed AgNPs- and Nano-TiO-Embedded Hydrogels as Novel Devices with Multiresponsive Antimicrobial Capability in Wound Healing.

Two antimicrobial agents such as silver nanoparticles (AgNPs) and titanium dioxide (TiO) have been formulated with natural polysaccharides (chitosan or alginate) to develop innovative inks for the rapid, customizable, and extremely accurate manufacturing of 3D-printed scaffolds useful as dressings in the treatment of infected skin wounds. Suitable chemical-physical properties for the applicability of these innovative devices were demonstrated through the evaluation of water content (88-93%), mechanical strength (Young's modulus 0.23-0.

From Au to Au: Tailored Synthesis of Superatomic Di-NHC/PPh-Stabilized Molecular Gold Nanoclusters.

Herein, we report a new method to synthesize molecular gold nanoclusters (AuNCs) stabilized by phosphine (PR) and di-N-heterocyclic carbene (di-NHC) ligands. The interaction of di-NHC gold(I) complexes, with the general formula [(di-NHC)AuCl] with well-known [Au(PPh)Cl]Cl clusters provides three new classes of AuNCs through a controllable reaction sequence. The synthesis involves an initial ligand metathesis reaction to produce [Au(di-NHC)(PPh)Cl] (type clusters), followed by a thermally induced rearrangement/metal complex addition with the formation of Au clusters [Au(di-NHC)(PPh)Cl] (type clusters).

A Adenosine Receptor Antagonists: Are Triazolotriazine and Purine Scaffolds Interchangeable?

The A adenosine receptor (AAR) is one of the four subtypes activated by nucleoside adenosine, and the molecules able to selectively counteract its action are attractive tools for neurodegenerative disorders. In order to find novel AAR ligands, two series of compounds based on purine and triazolotriazine scaffolds were synthesized and tested at ARs. Compound was also tested in an in vitro model of neuroinflammation.

A Reinterpretation of the Imidazolate Au(I) Cyclic Trinuclear Compounds Reactivity with Iodine and Methyl Iodide with the Perspective of the Inverted Ligand Field Theory.

Coinage metal cyclic trinuclear compounds (CTCs) are an emerging class of metal coordination compounds that are valuable for many fine optoelectronic applications, even though the reactivity dependence by the different bridging ligands remains somewhat unclear. In this work, to furnish some hints to unravel the effect of substituents on the chemistry of Au(I) CTCs made of a specific class of bridging ligand, we have considered two imidazolate Au(I) CTCs and the effect of different substituents on the pyrrolic N atoms relative to classic metal oxidations with I or by probing electrophilic additions. Experimental suggestions depict a thin borderline between the addition of MeI to the N-methyl or N-benzyl imidazolyl CTCs, which afford the oxidized CTC in the former and the ring opening of the CTC and the formation of carbene species in the latter.

Dinuclear gold(I) complexes with -phosphanyl, N-heterocyclic carbene ligands: synthetic strategies, luminescence properties and anticancer activity.

A small library of dinuclear gold(I) complexes with the title ligands has been prepared, encompassing neutral, mono- and dicationic complexes. The luminescence properties of the complexes in the solid state have been evaluated, and it turns out that neutral and monocationic complexes not presenting a rigid metallamacrocyclic structure can exhibit rather strong emissions that extend towards the red region of the visible spectrum. The anticancer activity of the complexes has been also preliminarly evaluated; cytotoxicity seems to correlate with complex lipophilicity, whereas selectivity towards cancer cells can be apparently enhanced upon a judicious choice of the ligands.

Synthesis and characterization of bipyridine cobalt(ii) complex modified graphite screen printed electrode: an electrochemical sensor for simultaneous detection of acetaminophen and naproxen.

The new Co(ii) compound [Co(5,5'-dmbpy)(NCS)] (a1) was prepared by reacting Co(NO)·6HO, 5,5'-dimethyl-2,2'-bipyridine ligand, and Na(SCN). The nano-scale size of [Co(5,5'-dmbpy)(NCS)] (a1) was synthesized using sonochemical process. The size of the nanoparticles (a2) was ∼13 ± 2 nm.

Toxic metal sequential sequestration in water using new amido-aminoacid ligand as a model for the interaction with polyamidoamines.

Polyamidoamines are low cost and easily synthesized materials that may find applications in cations sequestration and water treatment. In this paper a new amido-aminoacid ligand containing methionine has been designed as a monomeric model of the corresponding polyamidoamine. The amido-aminoacid ligand has been synthesized in high yield, by reacting acrylamide and methionine via aza-Michael addition in water and mild temperature conditions.

Three-Dimensional (3D) Printed Silver Nanoparticles/Alginate/Nanocrystalline Cellulose Hydrogels: Study of the Antimicrobial and Cytotoxicity Efficacy.

Here, a formulation of silver nanoparticles (AgNPs) and two natural polymers such as alginate (ALG) and nanocrystalline cellulose (CNC) was developed for the 3D printing of scaffolds with large surface area, improved mechanical resistance and sustained capabilities to promote antimicrobial and cytotoxic effects. Mechanical resistance, water content, morphological characterization and silver distribution of the scaffolds were provided. As for applications, a comparable antimicrobial potency against and was demonstrated by in vitro tests as function of the AgNP concentration in the scaffold (Minimal Inhibitory Concentration value: 10 mg/mL).

Correction: Quality of life under extended continuous versus intermittent adjuvant letrozole in lymph node-positive, early breast cancer patients: the SOLE randomised phase 3 trial.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Ag-functionalized nanocrystalline cellulose for paper preservation and strengthening.

Waste paper is an environmentally friendly source of cellulosic material. Here we propose a new treatment based on nanocrystalline cellulose (CNC) for paper preservation and consolidation. Suspensions of CNC were prepared by sulfuric acid hydrolysis using waste paper as cellulose source (CNC) and compared with CNC from cotton linter (CNC).

Structural and Luminescent Properties of Homoleptic Silver(I), Gold(I), and Palladium(II) Complexes with NHC-NHC Heteroditopic Carbene Ligands.

Novel silver(I), gold(I), and palladium(II) complexes were synthesized with bidentate heteroditopic carbene ligands that combine an imidazol-2-ylidene (NHC) with a 1,2,3-triazol-5-ylidene (NHC) connected by a propylene bridge. The silver(I) and gold(I) complexes were dinuclear species, [M(NHC-NHC)](PF) (M = Ag or Au), with the two bidentate ligands bridging the metal centers, whereas in the palladium(II) complex [Pd(NHC-NHC)](PF), the two ligands were chelated on the same metal center. Because of the presence of two different carbene units, isomers were observed for the gold(I) and palladium(II) complexes.

3D printed chitosan scaffolds: A new TiO support for the photocatalytic degradation of amoxicillin in water.

TiO-supported chitosan scaffolds (TiO/CS) are here proposed as promising material for wastewater treatment, in particular for the removal of pharmaceutical compounds. TiO/CS are tested for the amoxicillin photodegradation under UV/Vis irradiation. Amoxicillin (AMX) is an antibiotic of the beta-lactam family.

Quality of life under extended continuous versus intermittent adjuvant letrozole in lymph node-positive, early breast cancer patients: the SOLE randomised phase 3 trial.

Background: In the phase III SOLE trial, the extended use of intermittent versus continuous letrozole for 5 years did not improve disease-free survival in postmenopausal women with hormone receptor-positive breast cancer. Intermittent therapy with 3-month breaks may be beneficial for patients' quality of life (QoL).

Methods: In the SOLE QoL sub-study, 956 patients completed the Breast Cancer Prevention Trial (BCPT) symptom and further QoL scales up to 24 months after randomisation.

Bio-inspired consolidants derived from crystalline nanocellulose for decayed wood.

Novel bio-inspired materials derived from crystalline nanocellulose (CNC) have been tested as wood consolidants. A suspension of CNC, produced by acid hydrolysis of cellulose and used as such or mixed with lignin and/or siloxane derivatives (PDMS), was applied on rotted wood samples of Norway spruce. X-Ray diffraction analysis on CNC powder showed high crystallinity index.

Prevalence, characteristics, and treatment of fatigue in oncological cancer patients in Italy: a cross-sectional study of the Italian Network for Supportive Care in Cancer (NICSO).

Background: Fatigue is one of the most distressing symptoms of cancer patients. Its characteristics and impact on quality of life have not been fully explored and treatment of cancer-related fatigue in Italian oncological centers has not been codified.

Methods: A cross-sectional study was carried out on all patients attending for any reason the 24 participating centers in two non-consecutive days.

Hydrogen bonds and π-π inter-actions in two new crystalline phases of methyl-ene blue.

Two unprecedented solid phases involving the 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium cation, methyl-ene blue ( ), have been obtained and structurally characterized. In the crystals of 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium chloride dihydrate, CHNS·Cl·2HO () and 3,7-bis-(di-methyl-amino)-pheno-thia-zinium bis-ulfite, CHNS·HSO (), the cationic dye mol-ecules are planar and disposed in an anti-parallel mode, showing π-π stacking inter-actions, with mean inter-planar distances of 3.326 (4) and 3.

A square planar gold(iii) bis-(1,1'-dimethyl-3,3'-methylene-diimidazol-2,2'-diylidene) trication as an efficient and selective receptor towards halogen anions: the cooperative effect of AuX and XHC interactions.

Treatment of the tricationic gold(iii) [Au(MeImCHImMe)](PF) complex 1-3PF6 (Im = imidazol-2-ylidene) with excess halides affords complexes 1-3X (X = Cl, Br, and I), resulting from counter anion PF/X exchange. The H chemical shift of the CH groups and particularly that of the CH linker in DMSO-d are different in the three complexes, thus suggesting selective XHC interactions. Complex 13+ can therefore be used as a halide sensor in DMSO and water.

Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue.

The aromatic methylene blue cation (MB) shows unprecedented ligand behavior in the X-ray structures of the trigonal-planar (TP) complexes MBMCl (M = Cu, Ag). The two isostructural compounds were exclusively synthesized by grinding together methylene blue chloride and MCl solids. Only in the case of AuCl did the technique lead to a different, yet isoformular, Au derivative with separated MB and AuCl counterions and no direct N-Au linkage.

Stabilization of the cyclodecadiene derivative isofuranodiene by silver (I) coordination. Mechanistic and biological aspects.

The industrial extraction and further applications of isofuranodiene are limited because at room temperature it spontaneously converts to curzerene, a structurally less active isomer. This work definitively identified the structure of isofuranodiene in the solid state, showing the two methyl groups in syn position. In addition, two bioactive metal cations, namely, silver(I) and copper(II) ions, were used in the attempt to obtain the chemical stability of isofuranodiene: in the case of silver(I), a labile adduct was formed, while in the case of copper(II), a more stable 1:1 adduct was achieved.