An EPR, ENDOR and EIE study of gamma-irradiated poly (lactide-co-glycolide) polymers

Gamma radiation of poly (lactide-co-glycolide) raw polymers and processed microspheres under vacuum and at 77 K results in the formation of a series of free radicals. The resulting powder electron paramagnetic resonance (EPR) spectrum contains a distribution of several different radicals, depending on the annealing temperature, and is therefore difficult to interpret. By utilising the selectivity of the electron nuclear DOuble resonance (ENDOR) and associated ENDOR induced EPR (EIE) techniques, a more direct approach for the deconvolution of the EPR spectrum can be achieved. Using this approach, the radiolytically induced CH3 *CHC(O)R- chain scission radical was identified at 120 K by simulation of the EIE spectrum. At elevated temperatures (250 K), this radical decays considerably and the more stable radicals -O*CHC(O)-, CH3 *C(OR)C(O)- and CH3 *C(OH)C(O)- predominate. This work demonstrates the utility of the EIE approach to supplement and aid the interpretation of powder EPR spectra of radicals in a polymer matrix.     

On the ultrafast infrared spectroscopy of anion hydration shell hydrogen bond dynamics

Molecular Dynamics simulations are used to examine the title issue for the I-/HOD/D2O solution system in connection with recent ultrafast infrared spectroscopic experiments. It is argued that the long "modulation time" associated with the spectral diffusion of the OH frequency, extracted in these experiments, should be interpreted as reflecting the escape time of an HOD from the first hydration shell of the I- ion, i.e., the residence time of an HOD in this solvation shell. Shorter time features related to the oscillation of the OH ...I- hydrogen bond and the breaking and making of this bond are also discussed.     

Cyclodimerization versus Polymerization of Methyl Methacrylate Induced by N‐Heterocyclic Carbenes: A Combined Experimental and Theoretical Study

The activation behavior of two N‐heterocyclic carbenes (NHCs), namely, 1,3‐bis(isopropyl)imidazol‐2‐ylidene(NHCiPr) and 1,3‐bis(tert‐butyl) imidazol‐2‐ylidene (NHCtBu), as organic nucleophiles in the reaction with methyl methacrylate (MMA) is described. NHCtBu allows the polymerization of MMA in DMF at room temperature and in toluene at 50 °C, whereas NHCiPr reacts with two molecules of MMA, forming an unprecedented imidazolium–enolate cyclodimer (NHCiPr/MMA=1:2). It is proposed that the reaction mechanism occurs by initial 1,4‐nucleophilic addition of NHCiPr to MMA, generating a zwitterionic enolate 2 , followed by addition of 2 to a second MMA molecule, forming a linear imidazolium–enolate 3 (NHCiPr/MMA=1:2). Proton transfer, generating intermediate 5 , followed by cyclization and release of methanol yielded the aforementioned zwitterionic cyclodimer 1:2 adduct 7 , the molecular structure of which has been established by NMR spectroscopy, X‐ray diffraction, and mass spectrometry. This unexpected difference between NHCtBu and NHCiPr in the reaction with MMA (polymerization and cyclodimerization, respectively) can be rationalized by using DFT calculations. In particular, the nature of the NHC strongly influences the cyclodimerization pathway, the cyclization of 5 and the release of methanol are the discriminating step and limiting step, respectively. In the case of NHCtBu, both steps are strongly disfavoured compared with that of NHCiPr (energetic difference of around 14 and 9 kcal mol^?1, respectively), preventing the cyclization mechanism from a kinetic viewpoint. Moreover, addition of a third molecule of MMA in the polymerization pathway results in a lower activation barrier than that of the limiting step in the cyclodimerization pathway (difference of around 14 kcal mol^?1), in agreement with the formation of polymethyl methacrylate (PMMA) by using NHCtBu as nucleophile.     

Inorganic–Organic Heteropolyacid–Gold(I) Hybrids: Structures and Catalytic Applications

Gold(I)‐polyoxometalate hybrid complexes 1 – 4 ([PPh₃AuMeCN]_xH_4?xSiW₁₂O₄₀, x=1–4) were synthesized and characterized. The structure of the primary gold(I)–polyoxometalate 1 (x=1) was fully ascertained by XRD, FTIR, ³¹P and ²⁹Si magic‐angle spinning (MAS) NMR, mass spectroscopy, and SEM–energy dispersive X‐ray spectroscopy (EDX) techniques. Moreover, this complex exhibited better catalytic activity and selectivity compared with standard, homogeneous, gold catalysts in the new rearrangement of propargylic gem‐diesters.     

Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors

A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λ_max value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm² V^?1 s^?1 and the I_on/I_off value is greater than 10⁶.     

Void‐Assisted Ion‐Paired Proton Transfer at Water–Ionic Liquid Interfaces

At the water–trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P_14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H⁺) and deuterium ions (D⁺) was identified. Alkali metal cations (such as Li⁺, Na⁺, K⁺) did not undergo this transfer. H⁺/D⁺ transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP]^?, resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton‐coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents.     

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two‐step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β‐alanine betaine G5 , which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea‐based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen‐bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self‐associate. Remarkably, host 6 is able to perform solid–liquid as well as liquid–liquid extraction of G5 . Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.     

From the N‐Heterocyclic Carbene‐Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates

Among various N‐heterocyclic carbenes (NHCs) tested, only 1,3‐bis(tert‐butyl)imidazol‐2‐ylidene (NHC^tBu) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC‐catalyzed 1,4‐addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well‐defined α‐alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]₀/[ROH]₀ molar ratio, were ultimately obtained in N,N‐dimethylformamide at 25 °C. A hydroxyl‐terminated poly(ethylene oxide) (PEO‐OH) macro‐initiator was also employed to directly access PEO‐b‐PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC^tBu.     

BODIPY: A Highly Versatile Platform for the Design of Bimodal Imaging Probes

In molecular imaging, multimodal imaging agents can provide complementary information, for improving the accuracy of disease diagnosis or enhancing patient management. In particular, optical/nuclear imaging may find important preclinical and clinical applications. To simplify the preparation of dual‐labeled imaging agents, we prepared versatile monomolecular multimodal imaging probe (MOMIP) platforms containing both a fluorescent dye (BODIPY) and a metal chelator (polyazamacrocycle). One of the MOMIP was conjugated to a cyclopeptide (i.e., octreotide) and radiolabeled with ¹¹¹In. In vitro and in vivo studies of the resulting bioconjugate were conducted, highlighting the potential of these BODIPY‐based bimodal probes. This work also confirmed that the biovector and/or the bimodal probes must be chosen carefully, due to the impact of the MOMIP on the overall properties of the resulting imaging agent.     

Iron complexes as photoinitiators for radical and cationic polymerization through photoredox catalysis processes

Six iron complexes (FeCs) with various ligands have been designed and synthesized. In combination with additives (e.g., iodonium salt, N‐vinylcarbazole, amine, or chloro triazine), the FeC‐based systems are able to efficiently generate radicals, cations, and radical cations on a near UV or visible light‐emitting diode (LED) exposure. These systems are characterized by an unprecedented reactivity, that is, for very low content 0.02% FeC‐based systems is still highly efficient in photopolymerization contrary to the most famous reference systems (Bisacylphosphine oxide) illustrating the performance of the proposed catalytic approach. This work paves the way for polymerization in soft conditions (e.g., on LED irradiation). These FeC‐based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations and can operate through oxidation or/and reduction cycles. The photochemical mechanisms for the formation of the initiating species are studied using steady state photolysis, cyclic voltammetry, electron spin resonance spin trapping, and laser flash photolysis techniques. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 42–49