Total Synthesis and Revision of Stereochemistry of a Natural Benzo[g]isochromene Stereodiad Isolated from Rubia philippinensis.

This study presents a total synthesis and revision of the stereochemical configuration of the conformationally flexible natural product benzo[g]isochromene stereodiad alongside its diastereomeric counterparts. The highlights of the synthesis are the TiCl4-mediated diastereoselective aldol reaction, Pd-catalyzed lactonization, and Schmidt glycosidation. Our efforts using total synthesis disclosed herein proved that a previously assigned structure required revision.

Chiral LC method development: Stereo-selective separation, characterization, and determination of cabotegravir and related RS, RR, and SS isomeric impurities on coated cellulose-based chiral stationary phase by HILIC-LC and LC-MS.

The first, sensitive, and rapid chiral method was developed for enatioseperations and determination of cabotegravir and its enantiomeric impurities by using HPLC and LC-MS. Cabotegravir is an antiretroviral medication used for the treatment of HIV/AIDS approved by the food and drugs administration (FDA) in the year 2021. The cabotegravir chiral separation was achieved on the coated cellulose-tris (4-chloro-3-methyl phenyl carbamate) (CHIRALCEL OX-3R) column in HILIC mode and the total run time is less than 15 min. The effects of mobile phase composition, elution mode, and percentage of organic modifier as well as the effect of mobile phase-additives and column temperature were investigated on selectivity, resolution, and peak symmetry. The mobile phase consisted of acetonitrile and water with 0.1% (v/v) addition of formic acid additive with the flow rate of 1 mLmin-1. UV detection was carried out at 220 nm. The calibration curves of cabotegravir and its enantiomers were linear over the concentration range of 0.04-1.125 µgmL-1. The limits of detection and quantification for cabotegravir and its enantiomer (RS isomer) were ≤ 0.02 and ≤ 0.06, and the RR and SS-isomers limits were ≤ 0.02 and 0.03 µgmL-1 respectively. It was demonstrated that the proposed method is selective, precise, and robust. Finally, the validated method was applied for the determination and identification of cabotegravir and its chiral enantiomers in the bulk drugs by using HPLC and LC-MS techniques.

Assessment of interdisciplinary communication for Category 1 caesarean sections.

We assessed how often the urgency of Category 1 caesarean sections was incorrectly recorded by the anaesthetic and theatre teams. Category 1 caesarean sections were identified over a 15-month period (September 2010 to November 2011), from the daily audit of emergency caesarean sections undertaken by the obstetric team. The categories of urgency as recorded by the attending anaesthetist and theatre team were noted for each case. There were 236 Category 1 caesarean sections identified, of which 47 were incorrectly recorded as Category 2 by either the anaesthetist alone (34), the theatre team alone (1) or both (12). Where the category of urgency was correctly recorded, 11.6% of cases had a decision-to-delivery interval of more than 30 min compared with 27.7% of cases recorded as Category 2 (p = 0.01, Fisher's exact test).

Effects of caffeine on sperm characteristics after thawing and inflammatory response in the uterus after artificial insemination with frozen-thawed boar semen.

We previously reported that AI with frozen-thawed boar semen supplemented with caffeine increased the number of uterine sperm by inhibiting migration of polymorphonuclear leukocytes (PMNs) into the uterine lumen, and also improved fertility of gilts and sows. The objective of the present study was to determine the effects of the addition of caffeine to a thawing solution on postthaw sperm quality and uterine inflammatory response after AI with frozen-thawed boar semen. Incubation of frozen-thawed sperm in Modena solution supplemented with 10 mM caffeine for 90 minutes improved (P < 0.05) percentages of progressive motility, straightness, and linearity of sperm movement compared with no caffeine, without causing damage to plasma or acrosomal membranes. Gilts inseminated once with 2 × 10(9) frozen-thawed sperm suspended in Modena solution with or without caffeine, and gilts that did not receive AI, were slaughtered 4 hours later. Uteri were recovered for analysis of number of uterine PMNs and mRNA expression (quantitative reverse transcription polymerase chain reaction) of tumor necrosis factor-α, interleukin (IL)-1ß, IL-6, IL-8, monocyte chemoattractant protein-1, and cyclooxygenase 2 in the endometrium. Caffeine decreased (P < 0.05) both the number of total uterine PMNs and expression of IL-8 mRNA in the endometrium after AI. The amount of IL-8 and cyclooxygenase 2 mRNA after AI in the absence of caffeine were higher than samples from gilts that did not receive AI (P < 0.05), whereas there were no significant differences between treatments in expression levels of tumor necrosis factor-α, IL-1ß, IL-6, or monocyte chemoattractant protein-1 mRNA. Pregnancy rate in sows inseminated with sperm supplemented with caffeine (16 of 23; 70%) tended (P < 0.1) to exceed that without caffeine (12 of 26; 46%), but litter size was not affected. In conclusion, the addition of caffeine to the thawing solution inhibited migration of uterine PMNs, probably by downregulating IL-8 mRNA expression in the endometrium.

Diphallus associated with partial caudal duplication.

A 23-year-old man with similar pathology has presented in March 1998 for primary management of his diphallus and anorectal duplication.

EPR, ENDOR and TRIPLE resonance and MO studies on ubiquinones (Q-n): comparison of radical anions and cations of coenzymes Q-10 and Q-6 with the model compounds Q-2 and Q-0.

Radical anions and cations of the biologically important coenzymes Q-6 and Q-10, which have 6 and 10 unsaturated isoprene units in their side chains, respectively, have been generated in various solvents, and the results compared with those obtained for Q-0, a ubiquinone with no isoprene units, and for decylubiquinone Q-2 which has a saturated side chain. Hyperfine splitting constants (hfsc) of methyl and methoxy protons of the substituents in the quinone ring, and beta and gamma protons of the side chain were measured by EPR and ENDOR spectroscopy for both the radical anions and cations of Q-0, Q-6 and Q-10, and for the radical anion of Q-2. The relative signs of the hfsc were determined by general TRIPLE resonance spectroscopy. TRIPLE induced EPR (TIE) spectra were used for identification of the primary and secondary radicals of Q-10. The temperature dependence of the hfsc of the beta protons of Q-2 was different from those of Q-6 and Q-10. Fully optimised structures of Q-3 and Q-7 were obtained by performing semiempirical PM3 molecular orbital (MO) calculations for both neutral molecules and radical anions, neutral radicals and radical cations. Partial optimisation of the molecules was carried out for the side chain in a planar conformation. The folded conformation always had the minimum energy. Folding was so complete in the Q-7 series that the end of the side chain came into contact with the quinone ring, and small hfsc were detected in the PM3 calculations.