Probing Local pH Change during Electrode Oxidation of TEMPO Derivative: Implication of Redox-Induced Acidity Alternation by Imidazolium-Linker Functional Groups.

The chemical degradation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-based aqueous energy storage and catalytic systems is pH sensitive. Herein, we voltammetrically monitor the local pH (pHlocal) at a Pt ultramicroelectrode (UME) upon electro-oxidation of imidazolium-linker functionalized TEMPO and show that its decrease is associated with the greater acidity of the cationic (oxidized) rather than radical (reduced) form of TEMPO. The protons that drive the decrease in pH arise from hydrolysis of the conjugated imidazolium-linker functional group of 4-[2-(N-methylimidazolium)acetoxy]-2,2,6,6-tetramethylpiperidine-1-oxyl chloride (MIMAcO-T), which was studied in comparison with 4-hydroxyl-TEMPO (4-OH-T). Voltammetric hysteresis is observed during the electrode oxidation of 4-OH-T and MIMAcO-T at a Pt UME in an unbuffered aqueous solution. The hysteresis arises from the pH-dependent formation and dissolution of Pt oxides, which interact with pHlocal in the vicinity of the UME. We find that electrogenerated MIMAcO-T+ significantly influences pHlocal, whereas 4-OH-T+ does not. Finite element analysis reveals that the thermodynamic and kinetic acid-base properties of MIMAcO-T+ are much more favorable than those of its reduced counterpart. Imidazolium-linker functionalized TEMPO molecules comprising different linking groups were also investigated. Reduced TEMPO molecules with carbonyl linkers behave as weak acids, whereas those with alkyl ether linkers do not. However, oxidized TEMPO+ molecules with alkyl ether linkers exhibit more facile acid-base kinetics than those with carbonyl ones. Density functional theory calculations confirm that OH- adduct formation on the imidazolium-linker functional group of TEMPO is responsible for the difference in the acid-base properties of the reduced and oxidized forms.

Chemical and genomic diversity of six Lonicera species occurring in Korea.

Lonicera spp. (Caprifoliaceae) are important not only as a common medicinal herb in East Asia but also as one of the most problematic invasive species in North America. In the present study, we performed a systemic analysis of genomic and chemical diversity among six Lonicera species occurring in Korea, L. japonica, L. maackii, L. insularis, L. sachalinensis, L. praeflorens, and L. vesicaria, using chloroplast DNA whole genome shotgun (WGS) sequencing and LC-MS analyses. The phylogenetic and phylochemical relationships did not coincide with each other, but partial consistency could be found among them. InDel-based cDNA marker for authentication was developed based on the genome sequences. Flavonoids, iridoids, and organic acids were identified in the LC-MS analyses, and their inter-species distribution and localization were also revealed.

Argininosecologanin, a secoiridoid-derived guanidine alkaloid from the roots of Lonicera insularis.

A new secoiridoid-derived guanidine alkaloid, argininosecologanin (1), along with 12 known iridoids and secoiridoids (2-13), was isolated from the roots of Lonicera insularis. The structures of the isolated compounds were established by the spectroscopic analysis and comparison of their spectral data with previously reported data. Compound 1 was assigned as the first secoiridoid-derived guanidine alkaloid isolated as a natural product. A plausible biogenetic pathway for 1 is suggested based on its structural similarity to (E)-aldosecologanin (4).

Effects of Ovarian Cycle on Hemodynamic Responses during Dynamic Exercise in Sedentary Women.

This study tested the hypothesis that effects of the menstrual cycle on resting blood pressure carry over to dynamic exercise. Eleven healthy females were studied during the early (EP; low estrogen, low progesterone) and late follicular (LP; high estrogen, low progesterone) menstrual phases. Stroke volume (SV), heart rate (HR), cardiac output (CO), systolic blood pressure (SBP), diastolic blood pressure (DBP), and total vascular conductance (TVC) were assessed at rest and in response to mild and moderate cycling exercise during EP and LP. During EP, compared to LP, baseline SBP (111±1 vs. 103±2 mmHg), DBP (71±2 vs. 65±2 mmHg) and mean arterial pressure (MAP) (84±2 vs. 78±1 mmHg) were higher and TVC (47.0±1.5 vs. 54.9±4.2 ml/min/mmHg) was lower (p<0.05). During exercise, absolute values of SBP (Mild: 142±4 vs. 127±5 mmHg; Moderate: 157±4 vs. 144±5 mmHg) and MAP (Mild: 100±3 vs. 91±3 mmHg; Moderate: 110±3 vs. 101±3 mmHg) were also higher, while TVC was lower (Mild: 90.9±5.1 vs. 105.4±5.2 ml/min/mmHg; Moderate: 105.4±5.3 vs. 123.9±8.1 ml/min/mmHg) during EP (p<0.05). However, exercise-induced increases in SBP, MAP and TVC at both work intensities were similar between the two menstrual phases, even though norepinephrine concentrations were higher during LP. Results indicate that blood pressure during dynamic exercise fluctuates during the menstrual cycle. It is higher during EP than LP and appears to be due to additive effects of simultaneous increases in baseline blood pressure and reductions in baseline TVC.