Gold‐Catalyzed Intermolecular CS Bond Formation: Efficient Synthesis of α‐Substituted Vinyl Sulfones

A general method for the synthesis of α‐substituted vinyl sulfones makes use of a combination of a triazole gold complex and gallium triflate. This efficient C? S bond formation between simple terminal alkynes and sulfinic acids provides access to various α‐substituted vinyl sulfones.     

1,4-Cyclohexadiene with Pd/C as a rapid, safe transfer hydrogenation system with microwave heating

A method for the rapid, safe hydrogenation of alkenes and deprotection of benzyl ethers and carboxybenzyl amides is described using catalytic transfer hydrogenation under microwave heating conditions. Commonly available Pd/C catalyst is extremely effective with 1,4-cyclohexadiene as the hydrogen transfer source. In general, the reactions are complete within five minutes at 100 °C.     

Evaluation of blue and green absorbing proteorhodopsins as holographic materials

Transient holographic diffraction is observed for the green (GPR) and blue (BPR) absorbing proteorhodopsins (BAC31A8 and HOT75M1, respectively), as well as the GPR E108Q and BPR E110Q variants. In contrast to bacteriorhodopsin, where the metastable bR-M pair is responsible for generating diffraction, the pR and red-shifted N-like states fulfill that role in both the green and blue wild-type proteorhodopsins. The GPR E108Q and BPR E110Q variants, however, behave more similarly to their bacteriorhodopsin analogue, D96N, with diffraction arising from the PR M-state (strongly enhanced in both GPR E108Q and BPR E110Q). Of the four proteins evaluated, wild type (WT) GPR and GPR E108Q produce the highest diffraction efficiencies, etamax, at approximately 1% for a 1.7 OD sample. GPR E108Q, however, requires 1-2 orders of magnitude less laser intensity to generate eta equivalent to WT GPR and BR D96N under similar conditions (as compared to literature values). WT BPR requires lower actinic powers than GPR but diffracts only about 30% as well. BPR E110Q performs the most poorly of the four, with etamax < 0.05% for a 1.4 OD film. The Kramers-Kronig transformation and Koglenik's coupled wave theory were used to predict the dispersion spectra and diffraction efficiency for the long M-state variants. To a first approximation, the gratings formed by all samples decay upon discontinuing the 520 nm actinic beams with a time constant characteristic of the appropriate intermediate: the N-like state for WT GPR and BPR and the M-state for GPR 108Q and BPR E110Q.     

Methods for the characterization of Jet Propellent-8: vapor and aerosol

Jet Propellant‐8 (JP‐8) has been responsible for the majority of reported chemical exposures by the US Department of Defense. Concerns related to human exposure to JP‐8 are relatively new; therefore, there is a lack of literature data. Additionally, health effects related to the composition of the exposure have only recently been considered. Two major questions exist: (1) what is the compositional difference between the aerosol and vapor portions of JP‐8 under controlled conditions and (2) what is the most representative method to sample JP‐8 aerosol and vapor? Thirty‐seven standards, representing more than 40% of the mass of JP‐8, were used for characterization of the neat fuel, vapor and aerosol portions. JP‐8 vapor samples at a concentration of 1600 mg/m³ were prepared in Tedlar bags. A portion of the vapor samples was adsorbed on charcoal, Tenax and custom mixed phase sorbents. These samples were then extracted using organic solvent and analyzed using gas chromatography/mass spectrometry. The vapor samples extracted from the sorbent tubes were directly compared with a vapor bag. The samples collected using Tenax sorbent tubes were found to be most representative of the composition of the vapor bags. In another set of experiments, aerosolized JP‐8 was generated using a collision nebulizer. Aerosol samples were collected and the chemical composition was characterized. The entire aerosol distribution was collected on a glass filter, extracted into solvent, and analyzed by GC‐MS. Finally, the composition of the vapor and aerosol was compared. The vapor was found to represent the lower molecular weight components of JP‐8, while the aerosol was composed of higher molecular weight components. Therefore, the vapor and aerosol should be treated as two discrete forms of exposure to JP‐8. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of electron-donating and electron-withdrawing groups on peptide/single-walled carbon nanotube interactions

Nano-1, a designed peptide, has been demonstrated to efficiently disperse individual single-walled carbon nanotubes (SWNTs) by folding into an amphiphilic alpha-helix wherein the phenylalanine (Phe) residues on the hydrophobic face of the helix interact via pi-stacking with the aromatic surface of the SWNT. In this study, the ability of electron-donating (hydroxyl) and electron-withdrawing (nitro) groups on the phenyl ring of Phe to affect the interactions between the peptide and SWNTs is examined by substituting the Phe residues in the nano-1 sequence with tyrosine and p-nitro-phenylalanine, respectively. Atomic force microscopy measurements and optical absorption spectroscopy revealed that the ability to disperse individual SWNTs increases with increasing electron density of the aromatic residue on the hydrophobic face of the amphiphilic helical peptides. Scanning tunneling spectroscopy (STS) and Raman analyses were used to examine the effect of noncovalent protein functionalization on the electronic properties of SWNTs. Small shifts in the Raman G band peak for the peptide/SWNT composites, as well as weak features that appear near the Fermi energy (Ef) in the STS dI/dV spectra of the peptide-coated SWNTs, are suggestive of a weak charge-transfer interaction between the peptides and the SWNTs.     

Blue-emitting iridium complexes with substituted 1,2,4-triazole ligands: synthesis, photophysics, and devices

Neutral heteroleptic mononuclear iridium(III) complexes with (2,4-difluoro)phenylpyridine and different pyridine-1,2,4-triazole ligands were synthesized and fully characterized. We investigated the effects of substituents in the 5-position of the triazole ring on the photophysical and electrochemical behavior. Increasing the electron-withdrawing capabilities generally leads to a lowering of the HOMO level with a consequent slight widening of the HOMO-LUMO gap and a blue shift in emission. The complexes reported exhibit high emission quantum yields and long luminescent lifetimes, typical of iridium(III) complexes, and most of them show reversible redox processes in solution. Also, many of the complexes reported here have been obtained as single crystals suitable for X-ray crystallography. Two of the complexes were further tested as phosphorescent dyes in OLED devices and showed high external quantum efficiencies (~7%) and color points better than the "standard" for blue iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C2']picolinate (FIrpic). We also report the full electrochemical investigation of FIrpic in different solvents.     

Indium(III) trifluoromethanesulfonate as an efficient catalyst for the deprotection of acetals and ketals

Acetals and ketals are readily deprotected under neutral conditions in the presence of acetone and catalytic amounts of indium(III) trifluoromethanesulfonate (<0.8 mol %) at room temperature or mild microwave heating conditions to give the corresponding aldehydes and ketones in good to excellent yields.     

On maximal green sequences for type $$\mathbb {}$$ quivers

Given a framed quiver, i.e., one with a frozen vertex associated with each mutable vertex, there is a concept of green mutation, as introduced by Keller. Maximal sequences of such mutations, known as maximal green sequences, are important in representation theory and physics as they have numerous applications, including the computations of spectrums of BPS states, Donaldson–Thomas invariants, tilting of hearts in derived categories, and quantum dilogarithm identities. In this paper, we study such sequences and construct a maximal green sequence for every quiver mutation equivalent to an orientation of a type \(\mathbb {A}\) Dynkin diagram.     

Synthesis of cytotoxic cyanobactin,Wewakazole B

We report herein the synthesis of cytotoxic cyanobactin, Wewakazole B through an efficient solution-phase approach. The key steps of the synthesis are the macrocyclic lactamization of linear dodecapeptide and construction of two hexapeptides with three different substituted oxazole rings.