Controlling crosslinking in thermosets via chain transfer with monoterpenes

Renewable resources have been utilized to control the degree of crosslinking during ring‐opening metathesis polymerizations (ROMP). In this regard, the addition of monoterpenes to thermosets created a sustainable method for adjusting the physical properties and thermal stability. A number of monoterpenes with alkenes were examined as monofunctional reactants. The presence of these monoterpenes, such as β‐pinene, during the ROMP of dicyclopentadiene altered the degree of crosslinking and plasticized the thermoset. The resulting physical properties were tailored to obtain desired modulus and glass transition (T_g) temperatures. The influence of time, temperature, weight percent β‐pinene, and different metathesis catalysts was examined by dynamic mechanical analysis, thermogravimetric analysis, and FTIR spectroscopy. A comparison of β‐pinene with other monoterpenes, such as carvone, limonene oxide, myrcene, and d‐limonene, resulted in a reactivity profile for this general method. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of poly(N‐vinyl formamide) hydrogels—A potential alternative to polyacrylamide hydrogels

The synthesis and characterization of solution‐cast, molded gels of N‐vinyl formamide (NVF) has not been previously reported even though NVF is an isomer of acrylamide (AAm) and polyacrylamide (PAAm) hydrogels have many commercial applications. Aqueous NVF solutions were cross‐linked into gels using a novel cross‐linker, 2‐(N‐vinylformamido)ethylether, and the thermally‐activated initiator VA‐044. For a given formulation, PNVF gels swell up to twice that of PAAm gels cross‐linked with N,N′‐methylenebisacrylamide. From swelling and compression measurements, PNVF gels were found to be more hydrophilic than PAAm gels. Flory‐Huggins solubility parameters were χ = 0.38?₂ + 0.48 for PNVF and χ = 0.31?₂ + 0.49 for PAAm, where ?₂ is the polymer volume fraction. The shear moduli for PNVF and PAAm scale with ? and ? respectively, consistent with good solvent behavior, also suggesting PNVF is more hydrophilic than PAAm. Similarity of mechanical properties for both gels as a function of ?₂ suggests that network structures of PNVF and PAAm gels are similar. Fracture strains of both gels declined with ?₂ by the same linear function while fracture stresses were about 500 kPa regardless of formulation. Since NVF is a liquid monomer, less toxic than AAm and can be hydrolyzed to a cationic form, PNVF gels could become technologically significant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Low-frequency NMR with a non-resonant circuit

General expressions describing the refocused stimulated (RS) and refocused virtual (RV) electron spin echo envelope modulations (ESEEM) generated with the same basic four-pulse sequence are derived. It is shown that integration of the 3D time domain trace over the two "low-resolution" time intervals (those between the first and second and between the third and fourth microwave pulses) results in a dead time-free 1D ESEEM trace in the "high-resolution" dimension (i.e., the time interval between the second and third microwave pulses) that only contains harmonics with the fundamental frequencies of nuclear transitions. The practical implementation of the integrated RS ESEEM requires pulse swapping, which leads to unrecoverable distortions in the ESEEM traces and the resulting spectra. The integrated RV ESEEM is free from such distortions and represents a robust practical technique for obtaining dead time- and blind spots-free spectra of nuclear transitions, without homonuclear combination lines. As an application example, the integrated RV ESEEM was used to obtain the spectrum of a strongly-coupled proton of the OH ligand of the Mo(V) active center of the low-pH form of the molybdoenzyme sulfite oxidase.     

Poly(D,L-lactide-co-glycolide) nanoparticle agglomerates as carriers in dry powder aerosol formulation of proteins

A dry powder aerosol drug delivery system was designed with both nano- and microstructure to maximize the protein loading via surface adsorption and to facilitate delivery to the deep lung, respectively. Ovalbumin was employed as a model protein to adsorb to and controllably flocculate DOTAP-coated PLG nanoparticles into "nanoclusters" possessing low density microstructure. The mechanism of nanoparticle flocculation was probed by evaluating the effects of ionic strength, shear force, and protein concentration on the geometric and aerodynamic diameters of the nanoclusters as well as the protein adsorption efficiency. Salt ions were found to compete with ovalbumin adsorption to nanoparticles and facilitate flocculation; therefore, formulation of nanoclusters for inhaled drug delivery may require the lowest possible ionic strength to maximize protein adsorption. Additional factors, such as shear force and total protein-particle concentration can be altered to optimize nanocluster size, suggesting the possibility of regional lung delivery. Immediate release of ovalbumin was observed, and native protein structure upon release was confirmed by circular dichroism and fluorescence spectroscopy studies. Controlled flocculation of nanoparticles may provide a useful alternative to spray drying when formulating dry powders for pulmonary or nasal administration of protein therapeutics or antigens.     

The Unbalance of Set Systems

The unbalance of an intersecting family is defined as , where is the maximum degree of i.e. the maximum of over all vertices x. We show that the unbalance of a k-uniform intersecting family is at most when n ≥ 6k ³ and we determine all families achieving this bound.     

Design of Furan-Based Acceptors for Organic Photovoltaics

We explore a series of furan-based non-fullerene acceptors and report their optoelectronic properties, solid-state packing, photodegradation mechanism and application in photovoltaic devices. Incorporating furan building blocks leads to the expected enhanced backbone planarity, reduced band gap and red-shifted absorption of these acceptors. Still, their position in the molecule is critical for stability and device performance. We found that the photodegradation of these acceptors originates from two distinct pathways: electrocyclic photoisomerization and Diels–Alder cycloaddition of singlet oxygen. These mechanisms are of general significance to most non-fullerene acceptors, and the photostability depends strongly on the molecular structure. Placement of furans next to the acceptor termini leads to better photostability, well-balanced hole/electron transport, and significantly improved device performance. Methylfuran as the linker offers the best photostability and power conversion efficiency (>14 %), outperforming all furan-based acceptors reported to date and all indacenodithiophene-based acceptors. Our findings show the possibility of photostable furan-based alternatives to the currently omnipresent thiophene-based photovoltaic materials.     

Carbon-centered strong bases in phosphonium ionic liquids

Phosphonium ionic liquids (PhosILs), most notably tetradecyl(trihexyl)phosphonium decanoate (PhosIL-C(9)H(1)9COO), are solvents for bases such as Grignard reagents, isocyanides, Wittig reagents (phosphoranes), and N-heterocyclic carbenes (NHCs). The stability of the organometallic species in PhosIL solution is anion dependent. Small bases, such as hydroxide, react with the phosphonium ions and promote C-H exchange as suggested by deuterium-labeling studies. A method to dry and purify the ionic liquids is described and this step is important for the successful use of basic reagents in PhosIL. NHCs have been generated in PhosIL, and these persistent solutions catalyze organic transformations such as the benzoin condensation and the Kumada-Corriu cross-coupling reaction. Phosphoranes were generated in PhosIL, and their reactivity with various organic reagents was also tested. Inter-ion contacts involving tetraalkylphosphonium ions have been assessed, and the crystal structure of [(n-C(4)H(90)(4)P][CH(3)CO(2).CH(3)CO(2)H] has been determined to aid the discussion. Decomposition of organometallic compounds may also proceed through electron-transfer processes that, inter alia, may lead to decomposition of the IL, and hence the electrochemistry of some representative phosphonium and imidazolium ions has been studied. A radical derived from the electrochemical reduction of an imidazolium ion has been characterized by electron paramagnetic resonance spectroscopy.     

Biodegradable nanoparticle flocculates for dry powder aerosol formulation

Uncontrolled agglomeration presents a formidable encumbrance to nanoparticle formulation as a dry powder for inhalation therapy. Spray-drying and freeze-drying of nanosuspensions has demonstrated some success in creating dry powders composed of agglomerated nanoparticles with appropriate aerodynamic properties. These controlled drying processes, however, may require an undesirable amount of excipient to maintain an active therapeutic while generating dry powders and may not offer the desired control over agglomerate size and aerosolizability. As a potential alternative approach, a method for flocculating nanoparticles in solution followed by freeze-drying is reported. Biodegradable poly(DL-lactic-co-glycolic acid) nanoparticles were self-assembled into flocs via electrostatic interactions between nanoparticles coated with oppositely charged polyelectrolytes. The size of the nanoparticle flocs was readily controlled by manipulating the mixing ratio of charged nanoparticles. Freeze-drying the flocculated nanoparticles produced dry powders exhibiting low density (approximately 0.1 g/cm3), a weblike morphology, and desirable aerodynamic properties suited for dry powder aerosols.     

A regio- and stereoselective approach to quaternary centers from chiral trisubstituted aziridines

A thorough investigation of a regio- and stereospecific aziridine ring opening reaction presents new synthetic technology for the construction of a variety of quaternary beta-substituted-alpha-amino functional groups. Mild, metal-free reaction conditions allow for application in highly functionalized systems. This reaction has been applied to the challenging stereoselective formation of tertiary alkyl-aryl ethers. The strategy for the formation of these hindered ethers has been investigated using a variety of functionalized aziridines and phenols to determine the scope of the reaction. Other nucleophiles, such as thiolate, azide, and chloride, have also been examined to encompass the synthesis of a broader range of functionalities. This aziridine ring opening reaction manifold has demonstrated utility in assembling: beta-substituted-alpha-amino carboxamides, beta-substituted-alpha-amino esters, beta-substituted-alpha-amino silyl ethers, beta-thio-alpha-amino carboxamides, beta-azido-alpha-amino carboxamides, and beta-halo-alpha-amino carboxamides. Studies to probe the effect of the aziridine substitution patterns show that alkyl aziridines display similar reactivity to alkynyl aziridines, giving insight into mechanistic possibilities.     

Pincer-Supported Gallium Complexes for the Catalytic Hydroboration of Aldehydes,Ketones and Carbon Dioxide

Gallium hydrides stabilised by primary and secondary amines are scarce due to their propensity to eliminate dihydrogen. Consequently, their reactivity has received limited attention. The synthesis of two novel gallium hydride complexes HGa(THF)[ON(H)O] and H₂Ga[μ²-ON(H)O]Ga[ON(H)O] ([ON(H)O]²⁻=N,N-bis(3,5-di-tert-butyl-2-phenoxy)amine) is described and their reactivity towards aldehydes and ketones is explored. These reactions afford alkoxide-bridged dimers through 1,2-hydrogallation reactions. The gallium hydrides can be regenerated through Ga−O/B−H metathesis from the reaction of such dimers with pinacol borane (HBpin) or 9-borabicyclo[3.3.1]nonane (9-BBN). These observations allowed us to target the catalytic reduction of carbonyl substrates (aldehydes, ketones and carbon dioxide) with low catalyst loadings at room temperature.