3-Alkoxy-4-bromothiophenes: general synthesis of monomers and regio-selective preparation of two dimers

3-Alkoxy-4-bromothiophenes were synthesized in three steps from the readily available methyl 2-carboxylate-3-hydroxythiophene and two isomers of bithiophenes based on the 3-bromo-4-methoxythiophene moiety were regio-selectively prepared.     

Unprecedented Demonstration of Regioselective SEAr Reaction giving Unsymmetrical Regioregular Oligothiophenes

Aromatization of 4‐cyano‐3‐oxotetrahydrothiophene by sulfuryl chloride gives the new building block 4‐cyano‐3‐pyrrolidylthiophene, which forms unsymmetrical regioregular oligothiophenes with a strict alternation of the donor and acceptor groups along the conjugated system. The self‐coupling reactions that form the oligomers are shown to proceed by a regioselective electrophilic aromatic substitution mechanism involving a stabilized Wheland intermediate.     

Sinter‐Resistant Platinum Catalyst Supported by Metal–Organic Framework

Single atoms and few‐atom clusters of platinum are uniformly installed on the zirconia nodes of a metal‐organic framework (MOF) NU‐1000 via targeted vapor‐phase synthesis. The catalytic Pt clusters, site‐isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few‐atom clusters that depend upon synthesis conditions. Operando X‐ray absorption spectroscopy and X‐ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size‐selected clusters, including noble metals, on a high surface area support.     

A Mössbauer investigation of complexes of tin tetrahalides with ambidentate Lewis bases containing nitrogen,sulphur and oxygen

A series of 1 : 1 complexes was prepared with SnX₄ (X=Cl, Br, I) and the Lewis bases 2-mercaptobenzothiazole, 2-mercapto-1-methylimidazole, 2-aminothiazole, 2-acetylpyridine, and 2,2-bis(pyridyl)ketone. The latter two ligands yielded bidentate, N, O-bonded hexacoordinate complexes, whereas the other ligands produced monodentate, N-bonded pentaccoordinate species, as suggested by Mössbauer parameters, which correlate quite well with the IR spectroscopy data.     

Mannose‐6‐Phosphate Receptor: A Target for Theranostics of Prostate Cancer

The development of personalized and non‐invasive cancer therapies based on new targets combined with nanodevices is a major challenge in nanomedicine. In this work, the over‐expression of a membrane lectin, the cation‐independent mannose 6‐phosphate receptor (M6PR), was specifically demonstrated in prostate cancer cell lines and tissues. To efficiently target this lectin a mannose‐6‐phosphate analogue was synthesized in six steps and grafted onto the surface of functionalized mesoporous silica nanoparticles (MSNs). These MSNs were used for in vitro and ex vivo photodynamic therapy to treat prostate cancer cell lines and primary cell cultures prepared from patient biopsies. The results demonstrated the efficiency of M6PR targeting for prostate cancer theranostic.     

A Robust Infinite Zirconium Phenolate Building Unit to Enhance the Chemical Stability of Zr MOFs

A novel Zr‐chain based MOF, namely MIL‐163, was designed and successfully synthesized using a bis‐1,2,3‐trioxobenzene ligand. Endowed with large square‐shaped channels of 12 Å width, it shows remarkable water uptake (ca. 0.6 cm³ g^?1 at saturating vapor pressure) and a remarkable stability in simulated physiological media, where archetypical Zr carboxylate MOFs readily degrade.     

One‐Pot Synthesis of Well‐Defined Amphiphilic and Adaptative Block Copolymers via Versatile Combination of “Click” Chemistry and ATRP

Well‐defined amphiphilic PCL‐b‐PDMAEMA block copolymers were successfully synthesized by a combination of ATRP and “click” chemistry following either a commutative two‐step procedure or a straightforward one‐pot process using CuBr · 3Bpy as the sole catalyst. Compared to the traditional coupling method, combining ATRP and click chemistry even in a “one‐pot” process allows the preparation of PCL‐b‐PDMAEMA diblock copolymers characterized by a narrow molecular weight distribution and quantitative conversion of azides and alkynes into triazole functions. Moreover, the amphiphilic character of these copolymers was demonstrated by surface tension measurements and critical micellization concentration was calculated.