2-Methyltetrahydrofuran (2-MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP,FRP, and RAFT tandem polymerizations

2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines.     

Kinetic Investigation of Poly(ethylene glycol) Hydrogel Formation via Perfusion‐Based Frontal Photopolymerization: Influence of Free‐Radical Polymerization Conditions on Frontal Velocity and Swelling Gradients

Poly(ethylene glycol) diacrylate (PEGDA) hydrogels are extensively used as scaffolds in tissue engineering. The ability to spatially control hydrogel properties is critical for designing scaffolds that direct cell behavior and tissue regeneration. To this end, we have recently developed a polymerization technique, perfusion‐based frontal photopolymerization, to generate tunable gradients in PEG hydrogels. This study explores the effects of polymerization conditions on the velocity of the propagating front and its influence on gradients in hydrogel swelling. Alterations in photoinitiator perfusion rate result in the largest variations in frontal velocity and in the magnitude of the swelling gradient among all polymerization conditions investigated.

     

Efficient Synthesis of 2‐Aminothiazole‐4‐phenyl‐5‐acetamides via the Open Chain Tautomers of γ‐Keto Amides

A simple and efficient method is described for the synthesis of new functionalized 2‐aminothiazoles, the 2‐aminothiazole‐4‐phenyl‐5‐acetamides 5, in 67–96% yields based on an application of the Hantzsch synthesis. The method involves the reaction of thiourea with 3‐benzoyl‐3‐bromo‐propionamides 4 prepared from the corresponding 3‐benzoylpropionamides 3. The tautomeric structure of the γ‐keto amides 3 and 6 is directly related to the present study, because 2‐aminothiazoles 5 are readily obtained from the corresponding open chain γ‐keto amides 3.     

Oxone/Sodium Chloride: A Simple and Efficient Catalytic System for the Oxidation of Alcohols to Symmetric Esters and Ketones

An efficient method for the oxidation of alcohols is presented. The use of catalytic amounts of sodium chloride in combination with oxone allows the conversion primary aliphatic alcohols to symmetric esters. Secondary alcohols can be easily oxidized to ketones, and benzylic alcohols are converted to the corresponding aldehydes. The method is cost effective and enviromentally benign.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.     

Controlling the Surface Functionalization of Ultrasmall Gold Nanoparticles by Sequence-Defined Macromolecules

Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by ¹H NMR spectroscopy, ¹H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative ¹H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm² per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.     

Convergence properties and practical estimation of the probability of rank reversal in pairwise comparisons for multi-criteria decision making problems

In this paper, we address the impact of uncertainty introduced when the experts complete pairwise comparison matrices, in the context of multi-criteria decision making. We first discuss how uncertainty can be quantified and modeled and then show how the probability of rank reversal scales with the number of experts. We consider the impact of various aspects which may affect the estimation of probability of rank reversal in the context of pairwise comparisons, such as the uncertainty level, alternative preference scales and different weight estimation methods. We also consider the case where the comparisons are carried out in a fuzzy manner. It is shown that in most circumstances, augmenting the size of the expert group beyond 15 produces a small change in the probability of rank reversal. We next address the issue of how this probability can be estimated in practice, from information gathered simply from the comparison matrices of a single expert group. We propose and validate a scheme which yields an estimate for the probability of rank reversal and test the applicability of this scheme under various conditions. The framework discussed in the paper can allow decision makers to correctly choose the number of experts participating in a pairwise comparison and obtain an estimate of the credibility of the outcome.     

Functionalization of Graphene Oxide and its Biomedical Applications

Graphene oxide (GO) offers interesting physicochemical and biological properties for biomedicine due to its versatility, biocompatibility, small size, large surface area, and its ability to interact with biological cells and tissues. GO is a two-dimensional material of exceptional strength, unique optical, physical, mechanical, and electronic properties. Ease of functionalization and high antibacterial activity are two major properties identified with GO. Due to its excellent aqueous processability, amphiphilicity, surface functionalization capability, surface enhanced Raman scattering (SERS), and fluorescence quenching ability, GO chemically exfoliated from oxidized graphite is considered a promising material for biological applications. In addition, due to π-π* transitions, a low energy is required for electron movement, a property important in Biosensor and Bioimaging applications of GO. In this article, we present an overview of current advances in GO applications in biomedicine and discuss future perspectives. We conclude that GO is going to play a vital role in Biomedical applications in the near future.     

A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H₂P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C₆₀‐X‐NH₂ (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀ with those of BDP‐H₂P, BDP‐ZnP and BDP‐C₆₀, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H₂P or ZnP. This is then followed by an electron transfer to C₆₀, yielding the formation of the singlet charge‐separated states, namely BDP‐H₂P ^.+‐ C₆₀ ^.? and BDP‐ZnP ^.+‐ C₆₀ ^{. ?}. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.