Anthocyanins from the scarlet flowers of Anemone coronaria.

Three acylated anthocyanins were isolated from the scarlet flowers of Anemone coronaria 'St. Brigid Red' along with a known pigment, pelargonidin 3-lathyroside. The structures of the acylated pigments were based on a pelargonidin 3-lathyroside skeleton acylated at different positions with malonic acid. The first pigment was identified as pelargonidin 3-O-[2-(beta-D-xylopyranosyl)-6-O-(malonyl)-beta-D-galactopyranoside], the second was pelargonidin 3-O-[2-O-(beta-D-xylopyranosyl)-6-O-(methyl-malonyl)-beta-D-galactopyranoside], and the third was (6''-O-(pelargonidin 3-O-[2''-O-(beta-D-xylopyranosyl)-beta-D-galactopyranosyl]))((4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-O-tartatryl)malonate.

Acylated pelargonidin glycosides in red-purple flowers of Ipomoea purpurea.

Four acylated pelargonidin glycosides were isolated from the red-purple flowers of Ipomoea purpurea. The acylated anthocyanins were all based on pelargonidin 3-sophoroside-5-glucoside, acylated with caffeic acid and/or glucosylcaffeic acids. Three novel anthocyanins were elucidated to be pelargonidin 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)-caffeyl)- beta-D-glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-caffeyl)-beta-D- glucopyranosyl)-caffeyl)-beta-D-glucopyranoside]-5-O- [beta-D-glucopyranoside], pelargonidin 3-O-[2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-4-O-(6-O-(trans-caffeyl)-beta-D-glucospyranosyl)-ceffeyl )-beta-D- glucopyranoside]-5-O-[beta-D-glucopyranoside] and pelargonidin 3-O[2-O-(2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-caffeyl)-beta-D-glucopyranoside]-5-O-[beta-D-glucopyoside]. Another anthocyanin was pelargonidin 3-O-[2-O-(glucosylcaffeylglucosyl)-6-O-(caffeyl)-glucoside]-5-gluc oside, which was reported to be present in the red-purple flowers of Pharbitis nil. Apart from the second pigment cited, these are analogous pigments of the violet-blue Ipomoea anthocyanins which are composed of acylated cyanidin glycosides, instead of pelargonidin.

Acylated pelargonidin 3-sambubioside-5-glucosides in Matthiola incana.

Ten acylated pelargonidin 3-sambubioside-5-glucosides were isolated from the red-purple flowers of Matthiola incana, and also pelargonidin 3-glucoside was isolated from the brownish-red flowers of this plant. FAB mass measurements of 10 acylated anthocyanins gave their molecular ions [M]+ at 903-1195 m/z, which were based on acylated pelargonidin 3-sambubioside-5-glucosides with malonic acid, sinapic acid, p-coumaric acid, caffeic acid and/or ferulic acid. This was confirmed by the analysis of NMR spectra and the experiments of acid and alkaline hydrolysis. By spectral and chemical methods, seven of the 10 pigments were determined to be pelargonidin 3-O-[2-O-(2-O-(acyl-I)-beta-D-xylopyranosyl)- 6-O-(acyl-II)-beta-D-glucopyranoside]-5-O-[6-O-(malonyl)-beta-D- glucopyranoside], in which acyl moieties varied between sinapic, ferulic, caffeic and p-coumaric acids. The occurrence of these pigments was examined in 10 red-purple, 10 salmon-pink, three apricot and three copper colour cultivars of M. incana by HPLC. The acylated pelargonidin 3-sambubioside-5-glucosides were present as the dominant pigments in the red-purple, salmon-pink and apricot colour cultivars. On the other hand, pelargonidin 3-glucoside was present as a dominant anthocyanin in the copper colour cultivars and also pelargonidin 3-sambubioside-5-glucoside was confirmed by HPLC as a minor pigment in the copper colour flowers.

Acylated cyanidin glycosides in the violet-blue flowers of Ipomoea purpurea.

Six acylated cyanidin glycosides were isolated from violet-blue flowers of Ipomoea purpurea. These anthocyanins were all based on cyanidin 3-sophoroside-5-glucoside, acylated with caffeic acid and/or p-coumaric acid. Three anthocyanin structures were elucidated to be cyanidin 3-O(-)[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta -D-glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-caffeyl)-beta-D-glucopyran osyl) caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranoside], cyanidin 3-O(-)[2-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta-D-glucopyrano syl)- 6-O-(trans-caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranosid e d and cyanidin 3-O(-)[2-O-(6-O-(trans-caffeyl)-beta-D-glucopyranosyl)-6-O- (trans-caffeyl)-beta-D-glucopyranoside]-5-O(-)[beta-D-glucopyranoside]. These three anthocyanins were present in all 12 violet-blue flower strains as major pigments. The colours of these acylated antocyanins were stabler in neutral solution than their deacyl analogues.

[Changes in analgesic levels, plasma concentrations and epidurogram during long-term continuous epidural block].

The change of analgesic levels, plasma concentrations and the radiographical changes of epidural space due to continuous epidural block were studied in 54 patients receiving pain relief. All the patients received 2 ml per hour of 2% lidocaine or 0.5% bupivacaine via the catheter over two weeks. The effect of epidural block was determined on 1, 2, 4, 7, 10 and 14 days, the epidurogram was performed on 1, 7, 14 days, and plasma concentration of lidocaine or bupivacaine was measured on 1, 3, 7, 14 days. We removed catheters in 8 patients because of infection around the catheter, pain in the back during injection, the leakage of anesthetics, and spontaneous removal. The effects and plasma concentrations of epidural block decreased significantly after a week, and the mean segmental number of radiographic spread decreased significantly after two weeks. The decreasing effect or duration of epidural block was due to decrease in spread of anesthetics because of adhesion around the catheter in the epidural space. We conclude that the safety period of continuous epidural block is within 2 weeks.

[Use of ketamine combined with local anesthetics in epidural anesthesia].

Postoperative pain relief and sedation with epidural ketamine were studied. Twenty-four patients for elective upper abdominal surgery were divided into 4 groups. Epidural catheter was inserted into thoracic epidural space before induction of general anesthesia. In each group, either 0.25% bupivacaine 5 ml only, ketamine 0.1 mg.kg-1 + bupivacaine 5 ml, or ketamine 0.3 mg.kg-1 + bupivacaine 5 ml, or ketamine 0.5 mg.kg-1 + bupivacaine 5 ml was injected into epidural catheter for complaint of pain in recovery room. In ketamine injected groups, blood pressure and heart were unchanged, but respiration rate increased significantly. Patients in ketamine 0.3 or 0.5 mg.kg-1 injected groups, pain relief and sedation score were significantly intensified, but patients in ketamine 0.5 mg.kg-1 injected group, incidence of pain in the back during injection and headache was high. We conclude that epidural ketamine is useful for postoperative pain relief, and the superior dose of epidural ketamine is 0.3 mg.kg-1.

Acylated cyanidin 3-sambubioside-5-glucosides in Matthiola incana.

Four acylated cyanidin 3-sambubioside-5-glucosides were isolated from purple-violet flowers of Matthiola incana and their structures were determined by chemical and spectroscopic methods. Three acylated anthocyanins were cyanidin 3-O-(6-O-acyl-2-O-(2-O-sinapyl-beta-D-xylopyranosyl)-beta-D- glucopyranosides)-5-O-(6-O-malonyl-beta-D-glucopyranosides), in which the acyl group is p-coumaryl, caffeyl or ferulyl, respectively. The remaining pigment is free from malonic acid and was identified as cyanidin 3-O-(6-O-trans-ferulyl-2-O-(2- O-trans-sinapyl-beta-D-xylopyranosyl)-beta-D-glucopyranoside)-5-O- (beta-D-glucopyranoside). Analysis of the anthocyanin constituents in 16 purple-violet cultivars revealed that they contained the above triacylated anthocyanins in variable amounts as main pigments. An aromatic pair of pigments containing sinapic and ferulic acids are considered to produce an important intramolecular effect, making bluish colours in these flowers.

An acylated cyanidin glycoside in the red-purple flowers of x Laeliocattleya cv mini purple.

A new acylated anthocyanin was isolated from the red-purple flowers of x Laeliocattleya cv Mini Purple as one of the major anthocyanins. The structure of this pigment was determined to be cyanidin 3-O-[6-O-(malonyl)-beta-D-glucopyranoside]-7-O-[6-O-(trans-p- coumaryl)-beta-D-glucopyranoside]-3'-O-[6-O-[trans-4-O-[6-O-(trans-p- coumaryl)-beta-D-glucopyranosyl]-p-coumaryl]-beta-D-glucopyranoside] based on spectroscopic methods.

An acylated cyanidin glycoside from the red-purple flowers of Dendrobium.

A new acylated anthocyanin was isolated from the red-purple flowers of Dendrobium 'Pramot' (phalaenopsis type cv) as a major anthocyanin. The structure of this pigment was determined to be cyanidin-3-O-malonyl)-beta-D-glucopyranoside) 7,3'-di-O-(6-O-(4-O-(beta-D- glucopyranosyl)oxybenzoyl)-beta-D-glucopyranoside) mainly based on the spectroscopic evidence.

[Effects of hypotensive drugs on the function of red blood cell].

The shift of oxygen dissociation curve (ODC) and the function of red blood cell after the administration of hypotensive drugs prostaglandin E1 (PGE1), nicardipine (NIC), nitroglycerin, (TNG) were studied in 30 patients in whom mastectomy was performed. The author measured blood gases, blood sugar, L/P, ATP, the deformability of red blood cell, 2,3-DPG, and P50 in patients who had intravenous administration of low dose of PGE1 (0.05-0.1 microgram.kg-1 x min-1, n = 10), NIC (1.0-5.0 micrograms.kg-1 x min-1, n = 10) and TNG (0.5-1.0 microgram.kg-1 x min-1, n = 10). During the administration of these hypotensive drugs, A-aDO2 and blood sugar increased, but pH and L/P were unchanged. The deformability of red blood cell improved, and 2,3-DPG as well as P50 increased significantly after the administration of PGE1. PGE1, NIC, and TNG are all effective and safe drugs for hypotensive anesthesia. In particular, from the viewpoint of the function of red blood cell, it seems that PGE1 improves oxygen supply into tissues by improving deformability of red blood cell and by increasing P50.

An acylated cyanidin 3-sophoroside-5-glucoside in the violet-blue flowers of Pharbitis nil.

A new acylated anthocyanin was isolated from the violet-blue flowers of Pharbitis nil as a minor anthocyanin. The structure of this pigment was determined to be cyanidin 3-O-(2-O-(beta-D-glucopyranosyl)-6-O-(trans-4-O-(beta-D- glucopyranosyl)caffeyl)-beta-D-glucopyranosyl)-5-O-(beta-D-glucopyranosi de) based on spectroscopic methods.

Relationships between biological potency and electronic states of polychlorinated dibenzofurans and polychlorinated biphenyls.

It was found that the differences between the frontier molecular orbital energies (epsilon homo - epsilon lumo = delta epsilon) in polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) have a correlationship with the magnitude of the biological activity which is influenced by both the number and position of chlorine atom substituents on PCDFs and PCBs skeletons. Moreover, it was found that the delta epsilon's values of PCBs are classified into two types which coincide with the well-known classification of PCBs to types of 3-methylcholanthrene and phenobarbital according to their biological activities. The relationship between delta epsilon and biological activity in these xenobiotics suggests that the congeners having small delta epsilon values as 2,3,4,7,8-pentaCDF, 2,3,4,6,7-pentaCDF, 3,4,5,3',4'-pentaCB, and 3,4,5,3',4',5'-hexaCB form stable molecular complexes with an Ah-receptor, e.g. (2,3,4,7,8-PentaCDF-Ah-receptor), while the congeners having large delta epsilon values are strongly suggested to be unstable in a complex formation. Thus, this work presents an explanatory method to help understand the structure-activity relationship of the xenobiotics PCDFs and PCBs.

Berchemolide, a novel dimeric vanillic acid glucoside from Berchemia racemosa.

A new phenol glycoside named berchemolide was isolated together with (+)-catechin and (-)-epicatechin (as acetates), from the stems of Berchemia racemosa Sieb. et Zucc. (Rhamnaceae). The structure of berchemolide, having a dimeric dilactone structure with a 22-membered ring, was determined on the basis of spectral and chemical investigations. The conformation of berchemolide was calculated by MNDO (modified neglect of diatomic overlap).

Acylated pelargonidin glycosides in the red-purple flowers of Pharbitis nil.

Four acylated pelargonidin glycosides and pelargonidin 3-sophoroside-5-glucoside were isolated from 23 red-purple cultivars of Pharbitis nil. The acylated anthocyanins were all based on pelargonidin 3-sophoroside-5-glucoside and were identified as the 3-O-[2-O-(beta-D-glucopyranosyl)-6-O-(trans-caffeyl)-beta-D- glucopyranoside]-5-O-(beta-D-glucopyranoside), the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta- D-glucopyranosyl)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta- D-glucopyranosyl)-6-O-(trans-caffeyl)-beta-D-glucopyranoside]-5-O-(beta- D-glucopyranoside); and the 3-O-[2-O-(6-O-(trans-3-O-(beta-D-glucopyranosyl)caffeyl)-beta-D- glucopyranosyl)-6-O-(trans-4-O-(6-O-(trans-3-O-(beta-D- glucopyranosyl)caffeyl)- beta-D-glucopyranosyl)caffeyl)-beta-D-glucopyranoside]-5-O-(beta-D- glucopyranoside). By the analysis of these anthocyanin constituents variously in 23 cultivars, it was found that the red flower colour gradually changed into more bluish colour with increasing numbers of caffeic acid residues in the acylated pelargonidin glycosides. The stabilities of these anthocyanins increased in the order of increasing caffeyl substitution.

[Effects of mannitol on the function of red blood cells].

The effects of mannitol on the function of red blood cell were studied in 12 neurosurgical patients for 4 hours after intravenous administration of 2 g.kg-1 mannitol taking 30 min. After the administration of mannitol, osmotic pressure, Na and K in serum and of red blood cell were all altered. P50, 2, 3-DPG rose gradually and red blood cell deformity improved significantly. These results indicate that mannitol can shift oxyhemoglobin dissociation curve rightward, improve red blood cell deformity, and increase tissue oxygenation significantly. Mannitol administration not only decreases intracranial pressure but also improves peripheral circulation and oxygen transport during brain resuscitation.