External heavy atom effect on the triplet state of aromatic hydrocarbons: IV. Fluorene,triphenylene-d12 and coronene

The phosphorescence decay functions and spectra of ethanol solutions of triphenylene-d₁₂, coronene and fluorene were observed in the presence of different KI concentrations at 77 K. The analysis of the dependence of phosphorescence (T₁ → S₀) rate constant, k_PT, and intersystem crossing (T₁ ? S₀) rate constant, k_GT, on triplet energies E_T of aromatic molecules and on the distance between the heavy atom and the aromatic molecule show that the external heavy atom effects on k_PT and k_GT are essentially of the second and third order, respectively. The phosphorescence spectra of triphenylene and coronene show the presence of the third order contributions in the radiative transition, which involves the second triplet state of aromatic molecule.     

Reaction of 5,5-diphenyl-2-thiohydantoin with 1,2-dibromoethane.crystal and molecular structures of 2,3-dihydro-6,6-diphenylimi-dazo-[2,1-b]-thiazol-5(6h)-one and 2,3-dihydro-5,5-diphenylimi-dazo-[2,-1-b]-thiazol-6(5h)-one and their reactivity

The crystal and molecular structures of the title isomeric compounds $\text{1}$ and $\text{2}$, obtained by intramolecular N,S--dialkylation of 5,5-diphenyl-2-thiohydantoin with 1,2-dibro-moethane, have been determined from X-ray diffractometer data. 2,3-Dihydro-6,6-diphenylimidazo-[2,1-b]-thiazol-5(6H)-one $\text{1}$ crystallizes in space group P2₁2₁2₁ with a=11.376(3), b=12,255(5), c=8.434(3) Å and Z=4. Crystals of $\text{2}$, containing one molecule of benzene, are monoclinic,space group P2₁/c with a=11.539(6), b=10.242(3), c=16.353(5) Å, β=95.45(5)° and Z=4. In both cases a planar geometry of the two fused five-membered heterocyclic rings was found. The selected bond lengths in $\text{1}$ and $\text{2}$, as well as those analogous imidazothiazinones $\text{3}$ and $\text{4}$, were used to calculate E_HOSE (Harmonic Oscillation Stabilization Energy). The problem of stability and chemical reactivity of compounds $\text{1}$ to $\text{4}$ is also discussed.     

2-Aroylbenzoic acids—VIII: The synthesis and some reactions of 2-aroylbenzoic acids from m-chlorophenol

The syntheses of the novel 2-(4′-chloro-2′-hydroxybenzoyl) benzoic acid 1 and 2-(2′-chloro-4′-hydroxybenzoyl)benzoic acid 2 are described and some of their reactions are given.     

Analysis of spasmodic dysphonia by aerodynamic and laryngostroboscopic measurements

Sequential assessment of laryngeal function using laryngostroboscopy and phonatory air flow assessment was carried out in 18 patients with spasmodic dysphonia (SD). Comparison was made between findings in patients before treatment (n = 18), after unilateral recurrent nerve block by lidocaine (n = 6), after bilateral injections of botulinum toxin (Botox) (n = 13), and prior to Botox reinjection (n = 3). Unilateral nerve block resulted in higher mean phonatory airflows than after bilateral Botox injections. Both unilateral nerve block and Botox injections increased fluctuant or alternating flow source (AC); however, unilateral nerve block resulted in more unmodulated airflow leakage. Phonation time on a single breath was longer than with Botox injection. Bilateral Botox injections resulted in better glottal closure, fewer instances of vocal fold level differences, and, better vocal fold vibrations with phase symmetry, as determined by laryngostroboscopy. Partial bilateral denervation using Botox resulted in laryngeal function, which appeared to be intermediate between that of tightly squeezed pretreatment status and a breathy voice with incomplete adduction after unilateral nerve block. Of all treatments assessed, bilateral partial denervation by Botox appeared to be the most physiologic in restoring normal vocal fold vibratory function and airflow.     

Selective polycarboxylation of semiconducting single-walled carbon nanotubes by reductive sidewall functionalization

The efficient and controllable synthesis, the detailed characterization, and the chemical postfunctionalization of polycarboxylated single-walled carbon nanotubes SWCNT(COOH)(n) are reported. This innovative covalent sidewall functionalization method is characterized by (a) the preservation of the integrity of the entire σ-framework of SWCNTs; (b) the possibility of achieving very high degrees of addition; (c) control of the functionalization degrees by the variation of the reaction conditions (reaction time, ultrasonic treatment, pressure); (d) the identification of conditions for the selective functionalization of semiconducting carbon nanotubes, leaving unfunctionalized metallic tubes behind; (e) the proof that the introduced carboxylic acid functionalities can serve as versatile anchor points for the coupling to functional molecules; and (f) the application of a subsequent thermal degradation step of the functionalized semiconducting tubes leaving behind intact metallic SWCNTs. Functional derivatives have been characterized in detail by means of Raman, UV-vis/nIR, IR, and fluorescence spectroscopy as well as by thermogravimetric analysis combined with mass spectrometry, atomic force microscopy, and zeta-potential measurements.     

Liquid-phase microextraction and desorption electrospray ionization mass spectrometry for identification and quantification of basic drugs in human urine

Hollow fibre liquid-phase microextraction (LPME) and desorption electrospray ionization mass spectrometry (DESI-MS) were evaluated for the identification and quantification of basic drugs in human urine samples. The selective extraction capabilities of three-phase LPME provided a significant reduction in the matrix effects otherwise observed in direct DESI-MS analysis of urine samples. Aqueous LPME extracts (in 10 mM HCl) were deposited on porous Teflon, dried at room temperature, and the dried spots were then analyzed directly with DESI-MS in full scan mode. Pethidine, diphenhydramine, nortriptyline, and methadone were used as model compounds for identification, and their limits of identification were determined to be 100, 25, 100, and 30 ng/mL, respectively. In a reliability test with 19 spiked urine samples, 100% of the positive samples containing the model drugs in concentrations at or above the limit of identification were identified. Diphenhydramine was used as a model compound for quantitative analysis with diphenhydramine-d(5) as an internal standard. The calibration curve was linear in the range 50-2000 ng/mL (R(2) = 0.992) with a limit of quantification at approximately 140 ng/mL. The intra- and inter-day relative standard deviations were <9.5%. In a reliability test with six spiked urine samples, deviations between the measured and the true values for diphenhydramine were in the range 0.2-22.9%.     

Diffusion-weighted imaging (DWI) of the spleen in patients with liver cirrhosis and portal hypertension

Objective

The purpose of this study was to assess the influence of liver cirrhosis and portal hypertension on diffusion coefficients of the spleen.

Material and Methods

We retrospectively evaluated 50 patients with liver cirrhosis and 50 patients without any history of liver disease who underwent magnetic resonance imaging of the upper abdomen, including echo planar diffusion-weighted imaging using b values of 50, 300 and 600 mm²/s. Spleen apparent diffusion coefficient (ADC), liver ADC, muscle ADC and normalized spleen ADC (defined as the ratio of spleen ADC to muscle ADC) were compared between cirrhotic patients and patients in the control group and correlated with Child–Pugh stages. Reproducibility was assessed by measuring interclass correlation coefficient (n = 11). Additionally, in eight patients, ADC measurements were performed 1 day before and 3 days after transjugular intrahepatic portosystemic shunt (TIPSS) implantation.

Results

Compared with control subjects, patients with cirrhosis and portal hypertension had significantly higher spleen ADCs (P = .0001). There was a statistically significant correlation between Child–Pugh grade and spleen ADC (Pearson correlation coefficient, observer 1 r = 0.6, P = .0001; observer 2 r = 0.5, P = .0001). After TIPSS implantation, we observed a reduction in spleen ADC values. Spleen ADC measurements showed a high reproducibility (interclass correlation coefficient 0.75, P = .001).

Conclusion

Our data suggest that different stages of liver cirrhosis and portal hypertension correlate with ADC values of the spleen. Furthermore, ADC values of the spleen decrease after TIPSS implantation. Further studies are required to understand the potential clinical values of these observations.     

4(5)-vinylimidazole by dehydrobromination of 1-triphenylmethyl-4-(2-bromoethyl)imidazole

1-Triphenylmethyl-4-(2-bromoethyl)imidazole undergoes elimination upon basic treatment providing an easy approach to 4(5)-vinylimidazole whereas the N-unsubstituted analogue leads only to substitution products.     

Stereochemical aspects of the reaction of dialkyl phosphates with amine in the presence of triphenylphospine and carbon tetrachloride

Activation of P-chiral dialkyl phosphates with triphenylphosphine-carbon tetrachloride involves intermediate phosphonium salt 1 which undergoes nucleophilic attack by aniline or pyridine with inversion of configuration at the chiral phosphorus atom.