Aryl Nitro Reduction with Iron Powder or Stannous Chloride under Ultrasonic Irradiation

The selective reduction of aryl nitro compounds in the presence of sensitive functionalities, including halide, carbonyl, nitrile, and ester substituents, under ultrasonic irradiation at 35 kHz is reported in yields of 39–98%. Iron powder proved superior to stannous chloride with high tolerance of sensitive functional groups and high yields of the desired aryl amines in relatively short reaction times. Simple experimental procedure and purification also make the iron reduction of aryl nitro compounds advantageous over other methods of reduction.     

Synthesis of Quinolines from N-Tosyl-1-azadienes

A route to aryl-substituted quinolines from N-tosyl 1-azadienes is described. The key steps are a [4 + 2] cycloaddition with benzyne followed by base treatment of the 1,4-dihydroquinoline product. The N-tosyl 1-azadienes were prepared from readily accessible cinnamaldehyde and chalcone substrates by condensation with p-TsNH₂.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Diamond electrode facilitated electrosynthesis of water and wastewater treatment oxidants

While diamond electrodes have been commonly used to generate ^?OH to treat a variety of persistent water and wastewater micropollutants, mass transfer limitations and the non-selective, short-lived nature of the ^?OH restrict the degradation to the solution at, or near, the electrode surface. However, diamond electrodes can generate oxidizing species that facilitate micropollutant degradation in the bulk water solution. These include persulfate, sulfate radicals, peroxodiphosphate, ferrate, permanganate, reactive chlorine species, hydrogen peroxide, and ozone, which have been reported during electrochemical treatment of water with diamond electrodes. Although still restricted to specialized applications, recent studies, summarized in this review, have proven the electrogeneration of these additional oxidant species to be effective. They have shown the adaptability and potential of diamond electrode-based water treatment to mitigate the presence of micropollutants in water.     

Rheological and Solubility Properties of Soy Protein Isolate

Soy protein isolate (SPI) powders often have poor water solubility, particularly at pH values close to neutral, which is an attribute that is an issue for its incorporation into complex nutritional systems. Therefore, the objective of this study was to improve SPI solubility while maintaining low viscosity. Thus, the intention was to examine the solubility and rheological properties of a commercial SPI powder at pH values of 2.0, 6.9, and 9.0, and determine if heat treatment at acidic or alkaline conditions might positively influence protein solubility, once re-adjusted back to pH 6.9. Adjusting the pH of SPI dispersions from pH 6.9 to 2.0 or 9.0 led to an increase in protein solubility with a concomitant increase in viscosity at 20 °C. Meanwhile, heat treatment at 90 °C significantly improved the solubility at all pH values and resulted in a decrease in viscosity in samples heated at pH 9.0. All SPI dispersions measured under low-amplitude rheological conditions showed elastic-like behaviour (i.e., G′ > G″), indicating a weak “gel-like” structure at frequencies less than 10 Hz. In summary, the physical properties of SPI can be manipulated through heat treatment under acidic or alkaline conditions when the protein subunits are dissociated, before re-adjusting to pH 6.9.     

Consistency of post-Newtonian waveforms with numerical relativity

General relativity predicts the gravitational wave signatures of coalescing binary black holes. Explicit waveform predictions for such systems, required for optimal analysis of observational data, have so far been achieved primarily using the post-Newtonian (PN) approximation. The quality of this treatment is unclear, however, for the important late-inspiral portion. We derive late-inspiral waveforms via a complementary approach, direct numerical simulation of Einstein's equations. We compare waveform phasing from simulations of the last approximately 14 cycles of gravitational radiation from equal-mass, nonspinning black holes with the corresponding 2.5PN, 3PN, and 3.5PN orbital phasing. We find phasing agreement consistent with internal error estimates for either approach, suggesting that PN waveforms for this system are effective until the last orbit prior to final merger.     

Diagnosis of suspicious breast lesions using an empirical mathematical model for dynamic contrast-enhanced MRI

The purpose of this study was to test whether an empirical mathematical model (EMM) of dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) can distinguish between benign and malignant breast lesions. A modified clinical protocol was used to improve the sampling of contrast medium uptake and washout. T(1)-weighted DCE magnetic resonance images were acquired at 1.5 T for 22 patients before and after injection of Gd-DTPA. Contrast medium concentration as a function of time was calculated over a small region of interest containing the most rapidly enhancing pixels. Then the curves were fitted with the EMM, which accurately described contrast agent uptake and washout. Results demonstrate that benign lesions had uptake (P<2.0 x 10(-5)) and washout (P<.01) rates of contrast agent significantly slower than those of malignant lesions. In addition, secondary diagnostic parameters, such as time to peak of enhancement, enhancement slope at the peak and curvature at the peak of enhancement, were derived mathematically from the EMM and expressed in terms of primary parameters. These diagnostic parameters also effectively differentiated benign from malignant lesions (P<.03). Conventional analysis of contrast medium dynamics, using a subjective classification of contrast medium kinetics in lesions as "washout," "plateau" or "persistent" (sensitivity=83%, specificity=50% and diagnostic accuracy=72%), was less effective than the EMM (sensitivity=100%, specificity=83% and diagnostic accuracy=94%) for the separation of benign and malignant lesions. In summary, the present research suggests that the EMM is a promising alternative method for evaluating DCE-MRI data with improved diagnostic accuracy.     

Behavioral Characteristics of Children With Vocal Fold Nodules

Vocal fold nodules (VNs) in children are benign, bilateral lesions occurring on the mid-membranous vocal folds. Repetitive phonotraumatic behavior leading to chronic vocal fold injury and repair is frequently cited as the primary etiology; however, specific behavioral characteristics may predispose some children toward intense and potentially phonotraumatic voice use, thereby contributing secondarily to VN formation. The purpose of this case-control study was to determine whether children with VNs possess unique behavioral characteristics that may predispose them to VN development. Parents of 26 children with VNs (20 boys, 6 girls, mean age=7.2 years, SD=2.5 years), and 29 vocally normal, medical controls (22 boys, 7 girls, mean age=6.7 years, SD=2.4), completed the Childhood Behavior Checklist (CBCL/4-18, Achenbach, 1991), a standardized parent-rating scale with strong psychometric properties. No significant between-group differences were detected on any of the behavior problem syndrome scales. Group differences approached significance for the individual items "screams a lot" and "teases a lot" (VN group > Controls). The VN group scored significantly higher than the controls on the "Social Scale," a compilation of positive ratings of the child's social activity, frequency of contacts with friends, behavior with others, and behavior by themselves. Observed outcomes were consistent with previous characterizations of children with VN as "outgoing" or "extroverted" but were not consistent with other claims that this population may be at risk for "aggressive," "attentional," or "impulsive" behavior problems.     

α-Amidoaldehydes as Substrates in Rhodium-Catalyzed Intermolecular Alkyne Hydroacylation: The Synthesis of α-Amidoketones

We show that readily available α-amidoaldehydes are effective substrates for intermolecular Rh-catalyzed alkyne hydroacylation reactions. The catalyst [Rh(dppe)(C₆H₅F)][BAr^F₄] provides good reactivity, and allows a broad range of aldehydes and alkynes to be used as substrates, delivering α-amidoketone products. High yields and high levels of regioselectivity are achieved. The use of α-amidoaldehydes as substrates establishes that 1,4-dicarbonyl motifs can be used as controlling groups in Rh-catalyzed hydroacylation reactions.     

Synthesis,Characterization, and Antiproliferative Activity of Novel Chiral [QuinoxP*AuCl2]+ Complexes

Herein is reported the synthesis of two Au(III) complexes bearing the (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (R,R-QuinoxP*) or (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (S,S-QuinoxP*) ligands. By reacting two stoichiometric equivalents of HAuCl₄.3H₂O to one equivalent of the corresponding QuinoxP* ligand, (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (1) and (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) were formed, respectively, in moderate yields. The structure of (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) was further confirmed by X-ray crystallography. The antiproliferative activities of the two compounds were evaluated in a panel of cell lines and exhibited promising results comparable to auranofin and cisplatin with IC₅₀ values between 1.08 and 4.83 µM. It is noteworthy that in comparison to other platinum and ruthenium enantiomeric complexes, the two enantiomers (1 and 2) do not exhibit different cytotoxic effects. The compounds exhibited stability in biologically relevant media over 48 h as well as inert reactivity to excess glutathione at 37 °C. These results demonstrate that the Au(III) atom, stabilized by the QuinoxP* ligand, can provide exciting compounds for novel anticancer drugs. These complexes provide a new scaffold to further develop a robust and diverse library of chiral phosphorus Au(III) complexes.