Biradical processes in reactions between benzyne and tropone

The title reactions were investigated experimentally and theoretically. The benzyne--tropone pair has been known to give a Diels?CAlder [4+2] cycloadduct. However, in the present experiment using two sources of benzyne, many unexpected products were obtained. In particular, a zwitterion with a C?CCl bond is strikingly a major product, the structure of which was determined by the X-ray analysis. The bond is formed by quenching the Cl atom from the solvent CH₂Cl₂, which demonstrates that the reactions proceed via radical processes. DFT calculations revealed the elementary processes of the reactions. The presence of the novel zwitterion in the solid state has been interpreted in terms of the permanent dipole?Cdipole attractions/interactions/stabilization.     

Development of a precise quantitative method for monitoring sirolimus in whole blood using LC/ESI–MS/MS

Sirolimus is used on patients after solid organ transplantation and on lymphangioleiomyomatosis (LAM) patients, and therapeutic drug monitoring is required in clinical practice. We have previously reported an accurate method for quantitative determination of sirolimus, but its sample preparation step was complicated. In this study, we developed a modified liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI–MS/MS) method for sirolimus quantification. A supported liquid extraction cartridge was used to purify sirolimus from whole blood and ion suppression was mostly prevented. The validation results met the acceptance criteria. This method was compared with the antigen conjugated magnetic immunoassay (ACMIA) and our previously reported method, using whole blood samples from LAM patients. Comparison of the Bland–Altman plots of the currently developed method and the previous method revealed no significant difference between the two methods (mean bias, −2.02%; 95% CI, −7.81–3.78). The values obtained using ACMIA were significantly higher than those obtained using the current method by 13.87% (95% CI, 6.49–21.25) owing to cross-reactivity. The degrees of cross reactivities in LAM patients and in organ transplant patients were similar, and our LC/ESI–MS/MS method precisely measured the blood concentrations of sirolimus.     

Synthesis of jadomycin A and related jadomycin aglycons: structural re-examination of jadomycins S and T may be needed

Jadomycin A and related jadomycin M and W aglycons were synthesized. Easy re-construction of 4-(hydroxymethyl)-1,3-oxazolidin-5-one system into an isomeric 1,3-oxazolidine-4-carboxylic acid system during the synthetic trial of jadomycin S aglycon requests us to more precisely re-examine the structures proposed for jadomycins S and T, derived from hydroxyl-containing amino acids of l-serine and l-threonine, respectively.     

Clinical value of routine use of thin-section 3D MRI using 3D FSE sequences with a variable flip angle technique for internal derangements of the knee joint at 3T

PurposeTo determine the clinical value of routine use of thin-section 3D MRI using 3D FSE sequences with a variable flip angle technique for internal derangements of the knee joint at 3 T.Method and MaterialsThirty-four knees in 34 patients suspected of having internal derangements of the knee joint were included. Following standard 2D MRI protocol including sagittal PDWI, T1WI and T2*WI, coronal fat-suppressed PDWI, and axial fat-suppressed PDWI with 3-4 mm thicknesses, fat-suppressed and water-excitation PDWI using 3D FSE sequences with a variable flip angle technique with 0.6 mm thickness were obtained in coronal plane and the three major planes with 1 mm thickness (3D MRI) was reformatted. The standard 2D MRI protocol and reformatted 3D MRI protocol (three sagittal 2D sequence images plus 3D MRI) were independently analyzed by two radiologists concerning presence or absence of lesions in the menisci, cartilage, and ligament. Interobserver agreements in both the MRI protocols were assessed by weighted-kappa coefficients. Regarding diagnostic accuracy, areas under the receiver operating characteristic curves (Az values) of both the MRI protocols were compared.ResultsThirty-eight meniscal lesions, 39 cartilage lesions, and 20 ligamentous lesions were surgically detected. Excellent interobserver agreements (kappa = 0.91–0.98) were seen in both the MRI protocols, with a slightly better tendency in the reformatted 3D MRI protocol. Average Az values in detection of the meniscal, cartilage, and ligamentous lesions were significantly higher in the reformatted 3D MRI protocol than in the standard 2D MRI protocol (p < 0.01 or p < 0.001).ConclusionRoutine use of reformatted thin-section 3D MRI using 3D FSE sequences with a variable flip angle technique may improve diagnostic accuracy and confidence in detection of internal derangements of the knee joint.     

Unexpected high regiocontrol in Heck reaction of fluorine-containing electron-deficient olefins—Highly regio- and stereoselective synthesis of β-fluoroalkyl-α-aryl-α,β-unsaturated ketones

Treatment of (E)-4,4,4-trifluoro-1-aryl-2-buten-1-one with various aryldiazonium salts in the presence of palladium catalyst gave the corresponding α-arylated Heck adducts with high regio- and stereoselectivity in good to high yields.     

Solid phase extraction of zinc(II) using a PVC-based polymer inclusion membrane with di(2-ethylhexyl)phosphoric acid (D2EHPA) as the carrier

A polymer inclusion membrane (PIM) is reported consisting of 45% (m/m) di(2-ethylhexyl)phosphoric acid (D2EHPA) immobilized in poly(vinyl chloride) (PVC) for use as a solid phase absorbent for selectively extracting Zn(II) from aqueous solutions in the presence of Cd(II), Co(II), Cu(II), Ni(II) and Fe(II). Interference from Fe(III) in the sample is eliminated by precipitation with orthophosphate prior to the extraction of Zn(II). Studies using a dual compartment transport cell have shown that the Zn(II) flux (2.58 × 10⁻⁶ mol m⁻² s⁻¹) is comparable to that observed for supported liquid membranes. The stoichiometry of the extracted complex is shown to be ZnR₂·HR, where R is the D2EHPA anion.     

Measurement of planar elongation stress and viscosity in step planar elongation flow for mobile viscoelastic fluids

We propose a new technique which can treat low viscous viscoelastic fluids and which can measure the start-up and relaxation behavior of elongational stress in step elongation rate flow. This new device consists of two parts: the squeeze cell and the optical analyzer. The squeeze cell generates the planar squeeze flow and causes the step planar elongational flow at the stagnation point. The optical system measures the transient behavior of both birefringence and orientation angle in the start-up and relaxation region at the stagnation point. In this paper, we demonstrate the two-dimensionality of the flow in the planar squeeze cell. Next, we evaluated the planar elongational stress and viscosity from optical results for Maxwell fluid. These results show good agreement with Maxwell model. Finally, we clarify the measurement accuracy from the measurement results in channels of various sizes.     

Convenient synthesis of a marine cyclopentanoid: untenone A

(±)-Untenone A, one of the marine cyclopentanoids, has been conveniently synthesized via (±)-cis-1-hexadecylcyclopent-2-en-1,4-diol 9 which has been produced from 1-hexadecylcyclopenta-1,3-diene 6 via photo-oxidation and the following reduction. The key step of the present synthesis is the selective alkylation of cyclopenta-1,3-diene to form 6. Optically active (−)- and (+)-untenone A have been prepared from (−)- and (+)-9, respectively, after enzymatic kinetic resolution of (±)-9.