Simultaneous determination of testosterone, cortisol, and dehydroepiandrosterone in saliva by stable isotope dilution on-line in-tube solid-phase microextraction coupled with liquid chromatography–tandem mass spectrometry

We have developed a simple and sensitive method for the simultaneous determination of testosterone (TES), cortisol (CRT), and dehydroepiandrosterone (DHEA) in saliva by automated online in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS) using a Discovery HS F5 column. The optimum in-tube SPME conditions were 25 draw/eject cycles of 40 μL of sample at a flow rate of 200 μL/min using a Supel-Q PLOT capillary column as an extraction device. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. The in-tube SPME LC–MS/MS method showed good linearity with correlation coefficients r?≥?0.9998 for TES, CRT, and DHEA using their respective stable isotope-labeled internal standards. The intra-day and inter-day precisions (relative standard deviations) were below 4.9 and 8.5 % (n?=?5), respectively. This method was successfully utilized to analyze TES, CRT, and DHEA in saliva samples without any other pretreatment or interference peaks, and the quantification limits (S/N?=?10) of TES, CRT and DHEA were about 0.01, 0.03 and 0.29 ng/mL saliva, respectively. The recoveries of these compounds spiked into saliva samples were each above 94 %. This method was applied to analyze changes in salivary TES, CRT, and DHEA levels resulting from stress and fatigue load.     

A convenient stereoselective synthesis of β-lactams from β-hydroxy-α-thioalkylesters prepared from Michael/aldol tandem reaction or stereoselective addition of thiols to the Baylis-Hillman adducts

A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular S_N2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the conversion to β-lactams afforded a diastereomeric mixture. As an alternative approach to prepare the tandem adducts, the stereoselective Michael addition of aliphatic thiols to Baylis-Hillman adduct was developed. The stereoselectivity was sensitive to the protective group at the hydroxyl group and TBS protection brought the most successful syn-selective formation of the tandem adducts. The procedure could be applied to the ketone derivatives of the Baylis-Hillman adduct but no selectivity was observed for the nitrile-Baylis-Hillman adducts. A similar conversion of the adduct provided desired β-lactams stereoselectively.     

From Infinite Chains according to 1∞[Zr(S2O7)4/2] in Zr(S2O7)2 to the unprecedented [Zr(S2O7)4]4– Anion in Ag4[Zr(S2O7)4]

The reaction of ZrCl₄ with oleum (65 % SO₃) in the presence of Ag₂SO₄ at 250 °C yielded colorless single crystals of Zr(S₂O₇)₂ [orthorhombic, Pccn, Z = 4, a = 709.08(6) pm, b = 1442.2(2) pm, c = 942.23(9) pm, V = 963.5(2) × 10⁶ pm³]. Zr(S₂O₇)₂ shows Zr⁴⁺ ions in an eightfold distorted square antiprismatic coordination of oxygen atoms belonging to four chelating disulfate units. Each S₂O₇^2– ion is connected to a further Zr⁴⁺ ion leading to chains according to ¹_∞[Zr(S₂O₇)_4/2]. The same reaction at a temperature of 150 °C resulted in the formation of Ag₄[Zr(S₂O₇)₄] [monoclinic, C2/c, Z = 4, a = 1829.35(9) pm, b = 704.37(3) pm, c = 1999.1(1) pm, β = 117.844(2)°, V = 2277.6(2) × 10⁶ pm³]. Ag₄[Zr(S₂O₇)₄] exhibits the unprecedented [Zr(S₂O₇)₄]^4– anion, in which the central Zr⁴⁺ cation is coordinated by four chelating disulfate units. Thus, in Ag₄[Zr(S₂O₇)₄] the ¹_∞[[Zr(S₂O₇)_4/2] chains observed in Zr(S₂O₇)₂ are formally cut into pieces by the implementation of Ag⁺ ions.     

A cost-scaling algorithm for minimum-cost node-capacitated multiflow problem

Mathematical Programming - Many practical integer programming problems involve variables with one or two-sided bounds. Dunkel and Schulz (A refined Gomory–Chvátal closure for polytopes...     

On the group extension of the transformation associated to non-archimedean continued fractions

Summary Let F_q be a finite field with q elements. We consider formal Laurent series of F_q -coefficients with their continued fraction expansions by F_q -polynomials. We prove some arithmetic properties for almost every formal Laurent series with respect to the Haar measure. We construct a group extension of the non-archimedean continued fraction transformation and show its ergodicity. Then we get some results as an application of the individual ergodic theorem. We also discuss the convergence rate for limit behaviors.     

Bis[iridium(I)] complex of inverted N-confused porphyrin

The reaction of N-confused tetraphenylporphyrin with IrCl(CO)2(p-toluidine) gave a novel bis[iridium(I)] complex, wherein the confused pyrrole ring took an inverted conformation.     

Transformation of peptide nanotubes into a vesicle via fusion driven by stereo-complex formation

Two types of peptide nanotubes, one is prepared from an amphiphilic peptide having a right-handed helix segment and the other from that having a left-handed helix segment, are shown to transform the morphology into a vesicle by membrane fusion due to stereo-complex formation between these helical segments.     

Ruthenocene‐Type Complexes of N‐Fused Porphyrins

Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp₂] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.