Spasmodic dysphonia and vocal fold paralysis:Outcomes of voice problems on work-related functioning

Patients at a university voice disorder clinic diagnosed with spasmodicdysphonia (SD, n = 68) or vocal fold paralysis (VFP, n = 57) reported vocal symptoms and adverse work outcomes in contrast to a nondisordered group (ND, n = 68). Patients with SD most frequently cited symptoms of effortfulness (57%) and weakness (54%), VFP cited hoarseness (70%) and weakness (60%), while the nondisordered reported hoarseness (28%). SD and VFP produced greater (p<.05) adverse work outcomes than the nondisordered in the past (SD: 65%, VFP: 41%, ND: 3%), potential future (SD: 78%, VFP: 65%, ND: 19%), and current job performance (SD: 64%, VFP: 46%, ND: 2%). These disorders significantly disrupt socioeconomic outcomes and research is needed to improve functional ability and quality of life.     

Unexpected single-step formation of 1,2-anti-heterodisubstituted calix[4]arenes upon alkylation of a tribenzoyl precursor

The selective preparation and complete structural characterization of a small series of 1,2-anti-heterodisubstituted calix[4]arenes has been accomplished. These compounds were obtained in two steps from unsubstituted p-tert-butylcalix[4]arene by tribenzoylation and a subsequent one-pot, two-step sequence involving alkylation with simultaneous partial deacylation, resulting in heterodisubstituted calixarenes carrying an alkyl and an aroyl group. The monoalkyl-tribenzoyl intermediate, prior to in situ deprotection, could also be isolated.     

Novel titanocene anti-cancer drugs derived from fulvenes and titanium dichloride

Starting from 6-(p−N,N-dimethylanilinyl)fulvene (1a) or 6-(pentamethylphenyl)fulvene (1b) [1,2-di(cyclopentadienyl)-1,2-di(p−N,N-dimethylaminophenyl)ethanediyl] titanium dichloride (2a) and [1,2-di(cyclopentadienyl)-1,2-bis(pentamethylphenyl)ethanediyl] titanium dichloride (2b) and their corresponding dithiocyanato complexes (3a, 3b) were synthesized. Titanocene 2b did not show a cytotoxic effect, but when 2a was tested against pig kidney carcinoma cells (LLC-PK) or human ovarian carcinoma cells (A2780/cp70) inhibitory concentrations (IC₅₀) of 2.7 × 10⁻⁴ and 1.9 ×  10⁻⁴ M, respectively, were observed.     

Synthesis of discodermolide intermediates from engineered polyketides

Key intermediates used in Smith’s total synthesis of discodermolide were synthesized from an engineered polyketide made via precursor feeding to genetically modified polyketide producing bacteria.     

Experimental and Computational Studies of the Molybdenum‐Flanking Arene Interaction in Quadruply Bonded Dimolybdenum Complexes with Terphenyl Ligands

To clarify the nature of the Mo?C_arene interaction in terphenyl complexes with quadruple Mo?Mo bonds, ether adducts of composition [Mo₂(Ar′)(I)(O₂CR)₂(OEt₂)] have been prepared and characterized (Ar′=Ar^Xyl₂, R=Me; Ar′=ArMes₂, R=Me; Ar′=Ar^Xyl2, R=CF₃) (Mes=mesityl; Xyl=2,6‐Me₂C₆H₃, from now on xylyl) and their reactivity toward different neutral Lewis bases investigated. PMe₃, P(OMe)₃ and PiPr₃ were chosen as P‐donors and the reactivity studies complemented with the use of the C‐donors CNXyl and CN₂C₂Me₄ (1,3,4,5‐tetramethylimidazol‐2‐ylidene). New compounds of general formula [Mo₂(Ar′)(I)(O₂CR)₂( L )] were obtained, except for the imidazol‐2‐ylidene ligand that yielded a salt‐like compound of composition [Mo₂(Ar^Xyl2)(O₂CMe)₂(CN₂C₂Me₄)₂]I. The Mo?C_arene interaction in these complexes has been analyzed with the aid of X‐ray data and computational studies. This interaction compensates the coordinative and electronic unsaturation of one of the Mo atoms in the above complexes, but it seems to be weak in terms of sharing of electron density between the Mo and C_arene atoms and appears to have no appreciable effect in the length of the Mo?Mo, Mo?X, and Mo? L bonds present in these molecules.     

Chemically and Biologically Harmless versus Harmful Ferritin/Copper–Metallothionein Couples

The simultaneous measurement of the decrease of available Fe^II ions and the increase of available Fe^III ions allowed the analysis of the ferroxidase activity of two distinct apoferritins. Although recombinant human apoferritin (HuFtH) rapidly oxidizes Fe^II to Fe^III, this iron is not properly stored in the ferritin cavity, as otherwise occurs in horse‐spleen H/L‐apoferritin (HsFt; H=heavy subunit, L=light subunit). Iron storage in these apoferritins was also studied in the presence of two copper‐loaded mammalian metallothioneins (MT2 and MT3), a scenario that occurs in different brain‐cell types. For HuFtH, unstored Fe^III ions trigger the oxidation of Cu–MT2 with concomitant Cu^I release. In contrast, there is no reaction with Cu–MT2 in the case of HsFt. Similarly, Cu–MT3 does not react during either HuFtH or HsFt iron reconstitution. Significantly, the combination of ferritin and metallothionein isoforms reported in glia and neuronal cells are precisely those combinations that avoid a harmful release of Fe^II and Cu^I ions.     

Scalable Synthesis of Piperazines Enabled by Visible‐Light Irradiation and Aluminum Organometallics

The development of more active C? H oxidation catalysts has inspired a rapid, scalable, and stereoselective assembly of multifunctional piperazines through a [3+3] coupling of azomethine ylides. A combination of visible‐light irradiation and aluminum organometallics is essential to promote this transformation, which introduces visible‐light photochemistry of main‐group organometallics and sets the basis for new and promising catalysts.     

Nitric oxide binding and photodelivery based on ruthenium(II) complexes of 4-arylazo-3,5-dimethylpyrazole

Two fluorescent ligands, 3,5-dimethyl-4-(6'-sulfonylammonium-1'-azonaphthyl)pyrazole (dmpzn, 1) and 3,5-dimethyl-4-(4'-N,N'-dimethylaminoazophenyl)pyrazole (dmpza, 2) were obtained by condensation of ketoenolic derivatives with hydrazine. 1 and 2 formed the novel dinuclear complexes [(H(2)O)(3)ClRu(micro-L)(2)RuCl(H(2)O)(3)] (3 or 4) and [(H(2)O)(NO)Cl(2)Ru(micro-L)(2)RuCl(2)(NO)(H(2)O)] (6 or 7) (where L 1 = 2 or , respectively) which were characterized by IR, NMR and elemental analysis. The nitrosyl complexes were prepared by bubbling purified nitric oxide through methanol solutions of the corresponding ruthenium(II) chloroderivative or by reaction of the appropriate ligands with Ru(NO)Cl(3). Complexes 3 and 4 were found to bind NO, resulting in an increase in fluorescence. Ligand 1 also formed the mononuclear nitrosyl complex [Ru(NO)(bpy)(2)(dmpzn)]Cl(2) (8) which released NO in water at physiological pH and in the solid state as revealed by fluorescence and IR measurements, respectively.     

Synthesis and stabilization of subnanometric gold oxide nanoparticles on multiwalled carbon nanotubes and their catalytic activity

Small gold nanoclusters in a very narrow size distribution (1.1 ± 0.5 nm) have been stabilized onto multiwalled carbon nanotubes (MWCNT). Theoretical studies supported by XPS and (16)O(2)/(18)O(2) isotopic exchange experiments have shown that, on small gold nanoparticles (0.9-1.5 nm), dissociation of molecular O(2) and formation of a surface oxide-like layer is energetically favorable and occurs at room temperature, while O(2) recombination and desorption involves a larger activation barrier. CO titration experiments and theoretical studies demonstrate that the reactivity of the oxidized particles toward CO does not only depend on particle size but also on oxygen coverage. The oxidation-reduction process described is reversible, and the oxidized nanoparticles are active in the epoxidation of styrene with air.     

Synthesis of cis- and trans-3-aminocyclohexanols by reduction of β-enaminoketones

We describe a protocol developed for the preparation of β-enaminoketones derived from 1,3-cyclohexanediones, and their subsequent reduction by sodium in THF-isopropyl alcohol to afford cis- and trans-3-aminocyclohexanols.