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We have structurally characterized a number of lithiated calix[4]arenes, where the bridge in the calix[4]arene is thia (-S-, LSH4), sulfinyl (-SO-, LSOH4), sulfonyl (-SO2-, LSO2H4), dimethyleneoxa (-CH2OCH2-, LCOCH4) or methylene (-CH2-, LH4). In the case of L4SH4, interaction with LiOtBu led to the isolation of the complex [Li8(L4S)2(THF)4]·5THF (1·5THF), whilst similar interaction of L4SOH4 led to the isolation of [Li6(L4SOH)2(THF)2]·5(THF) (2·5THF). Interestingly, the mixed sulfinyl/sulfonyl complexes [Li8(calix[4]arene(SO)(SO2)(SO1.68)2)2(THF)6]·8(THF) (3·8THF) and [Li5Na(LSO/3SO2H)2(THF)5]·7.5(THF) (4·7.5(THF) have also been characterized. Interaction of LiOtBu with LSO2H4 and LCOCH4 afforded [Li5L4SO2(OH)(THF)4]·2THF (5·2THF) and [Li6(LCOC)2(HOtBu)2]·0.78THF·1.22hexane (6·0.78THF·1.22hexane), respectively. In the case of LH4, reaction with LiOtBu in THF afforded a monoclinic polymorph [LH2Li2(thf)(OH2)2]·3THF (7·3THF) of a known triclinic form of the complex, whilst reaction of the de-butylated analogue of LH4, namely de-BuLH4, afforded a polymeric chain structure {[Li5(de-BuL)(OH)(NCMe)3]·2MeCN} n (8·2MeCN). For comparative catalytic studies, the complex [Li6(LPr)2(H2O)2]·hexane (9 hexane), where LPr2H2 = 1,3-di-n-propyloxycalix[4]areneH2, was also prepared. The molecular crystal structures of 1-9 are reported, and their ability to act as catalysts for the ring opening (co-)/polymerization (ROP) of the cyclic esters ε-caprolactone, δ-valerolactone, and rac-lactide has been investigated. In most of the cases, complex 6 outperformed the other systems, allowing for higher conversions and/or greated polymer M n.

Synthetic polymer surfaces provide an excellent opportunity for developing materials with inherent antimicrobial and/or biocidal activity, therefore representing an answer to the increasing demand for antimicrobial active medical devices. So far, biologists and material scientists have identified a few features of bacterial cells that can be strategically exploited to make polymers inherently antimicrobial. One of these is represented by the introduction of cationic charges that act by killing or deactivating bacteria by interaction with the negatively charged parts of their cell envelope (lipopolysaccharides, peptidoglycan, and membrane lipids). Among the possible cationic functionalities, the antimicrobial activity of polymers with quaternary ammonium centers (QACs) has been widely used for both soluble macromolecules and non-soluble materials. Unfortunately, most information is still unknown on the biological mechanism of action of QACs, a fundamental requirement for designing polymers with higher antimicrobial efficiency and possibly very low toxicity. This mini-review focuses on surfaces based on synthetic polymers with inherently antimicrobial activity due to QACs. It will discuss their synthesis, their antimicrobial activity, and studies carried out so far on their mechanism of action. [ABSTRACT FROM AUTHOR]

Photodynamic therapy (PDT) relies on the combined action of a photosensitizer (PS), light at an appropriate wavelength, and oxygen, to produce reactive oxygen species (ROS) that lead to cell death. However, this therapeutic modality presents some limitations, such as the poor water solubility of PSs and their limited selectivity. To overcome these problems, research has exploited nanoparticles (NPs). This project aimed to synthesize a PS, belonging to the BODIPY family, covalently link it to two NPs that differ in their lipophilic character, and then evaluate their photodynamic activity on SKOV3 and MCF7 tumor cell lines. Physicochemical analyses demonstrated that both NPs are suitable for PDT, as they are resistant to photobleaching and have good singlet oxygen (1O2) production. In vitro biological analyses showed that BODIPY has greater photodynamic activity in the free form than its NP-bounded counterpart, probably due to greater cellular uptake. To evaluate the main mechanisms involved in PDT-induced cell death, flow cytometric analyses were performed and showed that free BODIPY mainly induced necrosis, while once bound to NP, it seemed to prefer apoptosis. A scratch wound healing test indicated that all compounds partially inhibited cellular migration of SKOV3 cells. [ABSTRACT FROM AUTHOR]

The reactions of the titanium alkoxide [Ti(OR)4] (R = Me, nPr, iPr, tBu) with the acids 2,2′-Ph2C(X)(CO2H), where X = OH and NH2, i.e., benzilic acid (2,2′-diphenylglycolic acid, L1H2), and 2,2′-diphenylglycine (L2H3), have been investigated. The variation of the reaction stoichiometry allows for the isolation of mono-, bi-, tri or tetra-metallic products, the structures of which have been determined by X-ray crystallography. The ability of the resulting complexes to act as catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and r-lactide (r-LA) has been investigated. In the case of ε-CL, all catalysts except that derived from [Ti(OnPr)4] and L2H3, i.e., 7, exhibited an induction period of between 60 and 285 min, with 7 exhibiting the best performance (>99% conversion within 6 min). The PCL products are moderate- to high-molecular weight polymers. For r-LA, systems 1, 3, 4 and 7 afforded conversions of ca. 90% or more, with 4 exhibiting the fastest kinetics. The molecular weights for the PLA are somewhat higher than those of the PCL, with both cyclic and linear PLA products (end groups of OR/OH) identified. Comparative studies versus the [Ti(OR)4] starting materials were conducted, and although high conversions were achieved, the control was poor. [ABSTRACT FROM AUTHOR]

The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(i) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation. [ABSTRACT FROM AUTHOR]

The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(i) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation. [ABSTRACT FROM AUTHOR]

Interaction of [Sc(OR)3] (R = iPr or triflate) with p-tert-butylcalix[n]arenes, where n = 4, 6, or 8, affords a number of intriguing structural motifs, which are relatively non-toxic (cytotoxicity evaluated against cell lines HCT116 and HT-29) and a number were capable of the ring opening polymerization (ROP) of cyclohexene oxide.

Carbene transition-metal complexes have become a prevalent family of catalysts enabling numerous organic transformations. Their facile synthetic access is a matter of great importance. To this end, the Cu(I) -NHC transfer methodology has emerged as a powerful alternative presenting attractive advantages over other methods. Herein, we report the remarkable ability of copper to transfer not only NHCs but also other types of carbenes such as abnormal NHCs (aNHCs), cyclic (alkyl)(amino)carbenes (CAACs), and mesoionic carbenes (MICs) to various transition metal precursors., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)