Molecular Structure of Gardenia Blue Pigments by Reaction of Genipin with Benzylamine and Amino Acids.

Genipin was reacted with benzylamine and several amino acids to prepare gardenia blue (GB). The time-course of GB formation with benzylamine was monitored by high-performance liquid chromatography (HPLC), liquid chromatography time-of-flight mass spectrometry (LC-TOFMS), and 1H and 13C NMR measurements. In this experiment, we determined the molecular structures of some intermediates using accurate masses and additional NMR techniques such as heteronuclear multiple bond correlation (HMBC). GBs with amino acids (GB-AAs) were characterized by both liquid and solid-state NMR measurements. Interestingly, many significant peaks appeared in the solid-state NMR spectra, although the 13C NMR spectra from solution samples did not show any distinct peaks. Therefore, we determined that GB-AAs had an alternating copolymer structure composed of methyne and 5H-2-pyrindine, which was substituted by amino acids at N atom and linked with methyne at 5 and 7 positions. To confirm this molecular structure, the pyrolysis gas chromatography-mass spectrometry (GC-MS) measurement of GB-AAs was carried out, and 5H-2-pyrindine and its methyl derivatives were formed as main pyrolysis products from the polymer chains.

Therapeutic Effects of Diagonal-Transcranial Direct Current Stimulation on Functional Recovery in Acute Stroke: A Pilot Study.

BACKGROUND: Peak neurologic recovery from acute stroke occurs within the first 3 months, and continues at a slower pace for 6 months. OBJECTIVE/HYPOTHESIS: The aim of this pilot study is to clarify the safety and feasibility of multiple diagonal-transcranial direct current stimulation (d-tDCS) sessions up to 3 months with electrodes placed diagonally over the lesional dorsolateral prefrontal cortex and contralesional primary motor cortex for upper limb hemiparesis in acute stroke. METHODS: Five patients with acute stroke (2 with intracerebral hemorrhage and 3 with cerebral infarction) with upper limb paresis participated. d-tDCS (1 mA, 20 min per day) combined with conventional rehabilitation was given starting 7-21 days after stroke onset. Each session consisted of 10 d-tDCS over 2 weeks and patients received 2 sessions in the acute phase and 2 sessions in the subacute phase for a total 40 treatments. Motor function was assessed using Fugl-Meyer Assessment for upper extremity (FMA-UE) before and after each session, and the period to achieve 70% of maximal potential recovery in FMA-UE was evaluated. RESULTS: All 5 patients completed the intervention and showed no adverse effects throughout the protocol. Of these, 3 (60%) achieved 70% predicted scores within 2 months. Regarding therapeutic gains of FMA-UE in each of the 10 sessions in the acute phase, 4 sessions showed great recovery, 3 sessions showed moderate recovery, and 3 sessions showed poor recovery. CONCLUSION: These findings suggest that d-tDCS over 3 months may be safe and feasible for acute stroke patients in the acute to subacute phases and have therapeutic potential to promote recovery of upper limb function, although further randomized, double-blind, sham-controlled trial is warranted with larger sample size.