Physicochemical properties of edible cricket oils: Implications for use in pharmaceutical and food industries.

The prevailing global market demands locally produced, sustainable oils for biomedical applications. This study focused on evaluating the quality of cricket-derived oils and meals from Scapsipedus icipe Hugel, Tanga, and Gryllus bimaculatus De Geer common delicacy in Africa, following standard methods for physicochemical properties, fatty acid composition, and phytochemicals (oxalates, phytates, tannins, and polyphenols). The cricket oils physicochemical properties aligned with Codex Alimentarius standards for edible oils, including low solidification temperature (< 2 °C), a high refractive index (1.46), and a specific gravity of 0.88. Notably, peroxide values (1.9 to 2.5 mg mEq O2/kg), acid values (1.1 to 2.2 mg KOH/g), and saponification values (234-246 mg KOH/g) all are indicative of lightness and unsaturated fatty acids. Nutritionally, cricket powder was rich in protein (56.8-56.9% -) and fat (31.7-33.5% -of dry matter), with significant amounts of essential omega-3 and omega-6 fatty acids. Predominant saturated and monounsaturated fatty acids were palmitic (23.9-31.2 mg/100 g-) and oleic acids (10.9-11.4 mg/100 g- of oil), respectively. Antioxidant values (48.0 to 65.0 mg/100 g), inferred from total polyphenols, suggests a stable oil with long shelf-life. These results highlight the promising and sustainable potential of cricket-derived oils for applications in the food and pharmaceutical industries.

Excessive gluconeogenesis causes the hepatic insulin resistance paradox and its sequelae.

Background: Hepatic insulin signaling suppresses gluconeogenesis but promotes de novo lipid synthesis. Paradoxically, hepatic insulin resistance (HIR) enhances both gluconeogenesis and de novo lipid synthesis. Elucidation of the etiology of this paradox, which participates in the pathogenesis of non-alcoholic fatty liver disease (NAFLD), cardiovascular disease, the metabolic syndrome and hepatocellular carcinoma, has not been fully achieved. Scope of review: This article briefly outlines the previously proposed hypotheses on the etiology of the HIR paradox. It then discusses literature consistent with an alternative hypothesis that excessive gluconeogenesis, the direct effect of HIR, is responsible for the aberrant lipogenesis. The mechanisms involved therein are explained, involving de novo synthesis of fructose and uric acid, promotion of glutamine anaplerosis, and induction of glucagon resistance. Thus, gluconeogenesis via lipogenesis promotes hepatic steatosis, a component of NAFLD, and dyslipidemia. Gluconeogenesis-centred mechanisms for the progression of NAFLD from simple steatosis to non-alcoholic steatohepatitis (NASH) and fibrosis are suggested. That NAFLD often precedes and predicts type 2 diabetes is explained by the ability of lipogenesis to cushion against blood glucose dysregulation in the earlier stages of NAFLD. Major conclusions: HIR-induced excessive gluconeogenesis is a major cause of the HIR paradox and its sequelae. Such involvement of gluconeogenesis in lipid synthesis rationalizes the fact that several types of antidiabetic drugs ameliorate NAFLD. Thus, dietary, lifestyle and pharmacological targeting of HIR and hepatic gluconeogenesis may be a most viable approach for the prevention and management of the HIR-associated network of diseases.

Effect of incorporation of snail meat powder on sensory attributes and consumer acceptability of sorghum-wheat buns.

Formulation of foods from -low-lysine cereals fortified with animal protein is a potentially sustainable approach to enhance protein quality in diet due to nutritional compensation while buns are valuable vehicles to deliver nutrients to human body because of their relatively noble eating quality and extended shelf life. The aim of this study was to evaluate the sensory attributes and consumer acceptability of sorghum-wheat buns containing snail meat powder (SMP). Buns were prepared by replacing 5, 10, 15, 20, and 25% of sorghum-wheat composite flour with SMP. Principal component analysis (PCA) revealed 99% total variation of 23 attributes for buns scored by a descriptive sensory panel, of which 98% was due to the proportion of SMP that replaced sorghum-wheat composite flour in buns and the remainder 1% was due to the buns' physical appearance. Compositing sorghum-wheat buns with SMP imparted positive consumer attributes of fine crumb, sponginess, and crumby texture. It also resulted in buns with reasonably high sensory acceptability as evaluated by 8- to 9-year-old school children. The buns can serve as supplementary rich sources of protein for alleviating the menace of protein energy malnutrition in sub-Saharan Africa.

From Farm to Fork: Crickets as Alternative Source of Protein, Minerals, and Vitamins.

Globally, there is growing interest to integrate cricket-based ingredients (flour) into food products to combat food and nutrition insecurity. However, there is lack of information on in-depth nutrient profile of the two cricket species (Scapsipedus icipe and Gryllus bimaculatus), which are the most widely consumed in Africa. Here we determined the nutrient composition of two cricket species and compared them with published records of key animal and plant sources. Our results revealed that the crude protein contents of S. icipe and G. bimaculatus were similar (56.8 and 56.9%, respectively) and comparable to those of animal protein sources. Both cricket species had balanced amino acid profiles that are superior to that of animal and plant sources, except for histidine and cysteine. The protein digestibility of S. icipe and G. bimaculatus ranged between 80 and 88%, which is comparable to that of common plant foods but slightly lower than that of animal proteins. The iron, Zinc, and potassium contents were considerably higher in both cricket species compared to that of plant and animal sources. The calcium contents of both crickets (S. icipe and G. bimaculatus) was superior to that of plant and animal origin except for kidney beans and eggs, respectively. Riboflavin, thiamine, and folic acid concentrations of S. icipe and G. bimaculatus were superior to that of the conventional sources. Vitamin A levels were significantly higher in S. icipe compared to G. bimaculatus. This implies that S. icipe and G. bimaculatus can adequately contribute to our daily required nutrient intake. Thus, integrating cricket flours into ready-to-eat food products would address some of the most pressing nutritional deficiency challenges that many developing countries have to grapple with, particularly high risk to serious health problems such as anemia, poor pregnancy outcomes, hypertension, increased risk of morbidity and mortality, stunted growth and impaired physical and cognitive development. We conclude that edible crickets present unique opportunities for improving food and nutritional insecurity status of both resource-poor and Western populations.

Mechanisms of the Regulation and Dysregulation of Glucagon Secretion.

Glucagon, a hormone secreted by pancreatic alpha cells, contributes to the maintenance of normal blood glucose concentration by inducing hepatic glucose production in response to declining blood glucose. However, glucagon hypersecretion contributes to the pathogenesis of type 2 diabetes. Moreover, diabetes is associated with relative glucagon undersecretion at low blood glucose and oversecretion at normal and high blood glucose. The mechanisms of such alpha cell dysfunctions are not well understood. This article reviews the genesis of alpha cell dysfunctions during the pathogenesis of type 2 diabetes and after the onset of type 1 and type 2 diabetes. It unravels a signaling pathway that contributes to glucose- or hydrogen peroxide-induced glucagon secretion, whose overstimulation contributes to glucagon dysregulation, partly through oxidative stress and reduced ATP synthesis. The signaling pathway involves phosphatidylinositol-3-kinase, protein kinase B, protein kinase C delta, non-receptor tyrosine kinase Src, and phospholipase C gamma-1. This knowledge will be useful in the design of new antidiabetic agents or regimens.

Effect of a nutrition education programme on the metabolic syndrome in type 2 diabetes mellitus patients at a level 5 Hospital in Kenya: "a randomized controlled trial".

BACKGROUND: Type 2 diabetes mellitus (T2D), is a life-threatening condition of global public health concern. It worsens in the presence of the metabolic syndrome (MetS), a complex disorder characterized by co-occurrence of at least three of such factors as hypertension, obesity, dyslipidemia and insulin resistance. However, lifestyle interventions reduce the risk of both MetS and T2D, and nutrition education can empower individuals on the appropriate, lifestyle changes. The aim of the current study was to evaluate the effect of a nutrition education programme, with and without inclusion of peer to peer support, on MetS in T2D patients. METHODS: This was a randomized controlled trial with two intervention groups and one control. One of the intervention groups involved a nutrition education programme with peer-to-peer support (NEP); the other involved only the education program, while the control received standard care. Each group had 51 participants. The nutrition education programme was conducted for 2 h per week for 8 weeks. In addition, the NEP had weekly peer-to-peer interactions for 8 weeks. All groups had follow-up sessions for 6 months. Data on MetS risk factors as well as food intake patterns and physical activity levels were taken at baseline and at different time points during the study. Analysis of Co-variance and regression were used in the analysis. RESULTS: The MetS prevalence improved in the NEP (90 to 52%) and NE (86 to 69%), while it worsened in C (88 to 91%). There was improvement in the mean values of the anthropometric parameters in the NEP and NE which worsened in the control group. There was a general improvement in mean values of blood lipids, fasting blood glucose and HbA1c in all the groups, with NEP showing the greatest improvements, followed by NE, except for triglycerides and HDL where the control group had better improvement than the NE. Changes in the anthropometric and metabolic indicators mirrored the changes in food intake patterns and physical activity, where the greatest improvements occurred in the NEP. CONCLUSIONS: Nutrition education with inclusion of peer to peer support was of clinical benefit in improving metabolic outcomes and reducing MetS in T2DM patients. TRIAL REGISTRATION: The study has been registered retrospectively by Pan African Clinical Trial Registry; Registration No: PACTR201910518676391.

Efficacy of compositing with snail meat powder on protein nutritional quality of sorghum-wheat buns using a rat bioassay.

BACKGROUND: Protein energy malnutrition (PEM) is an important health burden in most developing countries mainly in sub-Saharan Africa, where it contributes to high rates of child morbidity and mortality. This study evaluated the efficacy of compositing with snail meat powder (SMP) on protein nutritional quality of sorghum-wheat buns using a rat bioassay. Nine diets -seven isonitrogenous diets, based on six variations of buns and a reference diet made using skimmed milk powder, in addition to the basal diet meant to estimate the endogenous nitrogen excretion and a 16% protein rehabilitation diet - were fed to male weanling albino rats. Protein efficiency ratio (PER), and food efficiency ratio (FER), net protein retention ratio (NPRR), apparent protein digestibility (APD), and true protein digestibility (TPD), protein digestibility corrected amino acid score (PDCAAS), and digestible indispensable amino acid score (DIAAS) indices of protein quality were determined. RESULTS: Fortification with SMP significantly (P < 0.05) enhanced PER from 0.21% to 2.70%, FER from 0.02% to 0.27%, APD from 81.17% to 88.28%, and TPD from 87.48% to 95.38%. PDCAAS and DIAAS increased from 45% to 78% and 44% to 69% respectively in unfortified buns to buns fortified with 25% SMP. CONCLUSION: Complementary diets fortified with SMP promote growth and rehabilitate emaciated rats, whereas unfortified diet did not support weight gain. Thus, supplementation of buns with SMP might enhance a faster recovery in children affected by PEM. © 2020 Society of Chemical Industry.

Cellular Stresses and Stress Responses in the Pathogenesis of Insulin Resistance.

Insulin resistance (IR), a key component of the metabolic syndrome, precedes the development of diabetes, cardiovascular disease, and Alzheimer's disease. Its etiological pathways are not well defined, although many contributory mechanisms have been established. This article summarizes such mechanisms into the hypothesis that factors like nutrient overload, physical inactivity, hypoxia, psychological stress, and environmental pollutants induce a network of cellular stresses, stress responses, and stress response dysregulations that jointly inhibit insulin signaling in insulin target cells including endothelial cells, hepatocytes, myocytes, hypothalamic neurons, and adipocytes. The insulin resistance-inducing cellular stresses include oxidative, nitrosative, carbonyl/electrophilic, genotoxic, and endoplasmic reticulum stresses; the stress responses include the ubiquitin-proteasome pathway, the DNA damage response, the unfolded protein response, apoptosis, inflammasome activation, and pyroptosis, while the dysregulated responses include the heat shock response, autophagy, and nuclear factor erythroid-2-related factor 2 signaling. Insulin target cells also produce metabolites that exacerbate cellular stress generation both locally and systemically, partly through recruitment and activation of myeloid cells which sustain a state of chronic inflammation. Thus, insulin resistance may be prevented or attenuated by multiple approaches targeting the different cellular stresses and stress responses.

Metabolomic analyses to evaluate the effect of drought stress on selected African Eggplant accessions.

BACKGROUND: Drought stress is one of the main abiotic stresses that affect crops. It leads to biochemical changes that can have adverse effects on plant growth, development and productivity. African eggplants are important vegetable and fruit crops reported to adapt and thrive well under drought stress. The diversified metabolites arising due to stress have not been well defined. A gas chromatographic-mass spectrometric metabolomic approach was applied to characterize the effect of drought stress on metabolites at different stages of growth. Nineteen accessions were selected for analysis and drought was imposed by withholding water until soil moisture reached 60% field capacity. Fresh leaf tissues were sampled before stress, 2 and 4 weeks after stress and metabolite profiling done. RESULTS: Significant changes in metabolite content were observed, and potentially important metabolites with respect to stress responses were characterized. Proline, glutamate, sucrose, fructose and tricarboxylic acid cycle metabolites were shown to be positively correlated with stress. Principal component analysis showed a clear discrimination between the different accessions, growth stages and stress/control conditions. CONCLUSION: The results illustrate that drought stress has a significant impact on the concentrations of some metabolites, such as amino acids, sugars and organic acids, which may contribute to drought stress effects and tolerance. © 2017 Society of Chemical Industry.

The Contribution of Singlet Oxygen to Insulin Resistance.

Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR), and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER) stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo)-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses.

Carotenoid profiling of the leaves of selected African eggplant accessions subjected to drought stress.

African eggplants (Solanum aethiopicum and S. macrocarpon) are among the most economically important and valuable vegetable and fruit crops. They are a major source of biologically active nutritional substances and metabolites which are essential for plant growth, development, stress adaptation and defense. Among these metabolites are the carotenoids which act as accessory pigments for photosynthesis and precursor to plant hormones. Though African eggplants are known to be resistant to various abiotic stresses, the effect of these stresses on secondary metabolites has not been well defined. The objective of this study was to establish the effect of drought stress on carotenoid profiles of nineteen African eggplant accessions selected based on leaf and fruit morphological traits. Stress was achieved by limiting irrigation and maintaining the wilting state of the crops. Fresh leaves were sampled at different maturity stages; before stress, 2 weeks and 4 weeks after stress for carotenoid analysis. The fresh harvested leaf tissues were immediately frozen in liquid nitrogen and ground. Analysis was carried out using a Dionex HPLC machine coupled to Photo Array Detector and Chromeleon software package (Thermo Fisher Scientific Inc, Waltham, Massachusetts, USA). Major carotenoids viz;. Xanthophylls (neoxanthin, violaxanthin, zeaxanthin and lutein) and carotenes (ß-carotene and α-carotene), phytofluene, lycopene, phytoene as well as chlorophylls (chlorophyll-b and Chlorophyll-a) were targeted. The carotenoids increased with maturity stage of the crop. Although the stressed crops reported significantly decreased amount of carotenes, chlorophylls, neoxanthin and violaxanthin, the concentration of zeaxanthin increased with stress whereas lutein had no significant change. Chlorophyll-a was significantly high in all the control accessions. Two accessions reported significantly higher contents of carotenoids as compared to the other accessions. The results of this study indicate that water stress has significant impact on the concentration of some carotenoids and photosynthetic pigments. This will definitely add value to the study of stress tolerance in crops.

Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid.

Lipid oxidation-derived carbonyl compounds are associated with the development of various physiological disorders. Formation of most of these products has recently been suggested to require further reactions of oxygen with lipid hydroperoxides. However, in rat and human tissues, the formation of 4-hydroxy-2-nonenal is greatly elevated during hypoxic/ischemic conditions. Furthermore, a previous study found an unexpected result that the decomposition of a phosphatidylcholine (PC) bearing the 13-hydroperoxide of linoleic acid under a nitrogen atmosphere afforded 9-oxononanoyl-PC rather than 13-oxo-9,11-tridecadienoyl-PC as the main aldehydic PC. In the present study, products of the anaerobic decomposition of a PC bearing the 9-hydroperoxide of linoleic acid were analysed by electrospray ionization mass spectrometry. 9-Oxononanoyl-PC (ONA-PC) and several well-known bioactive aldehydes including 12-oxo-9-hydroperoxy-(or oxo or hydroxy)-10-dodecenoyl-PCs were detected. Hydrolysis of the oxidized PC products, methylation of the acids obtained thereby, and subsequent gas chromatography-mass spectroscopy with electron impact ionization further confirmed structures of some of the key aldehydic PCs. Novel, hydroxyl radical-dependent mechanisms of formation of ONA-PC and peroxyl-radical dependent mechanisms of formation of the rest of the aldehydes are proposed. The latter mechanisms will mainly be relevant to tissue injury under hypoxic/anoxic conditions, while the former are relevant under both normoxia and hypoxia/anoxia.

Effect of water stress on growth of three linseed (Linum usitatissimum L.) varieties.

Linseed (Linum usitatissimum L.) is an annual oil crop that accounts for approximately 1 % of the world's oilseed supplies. It produces seeds that are rich in the health-promoting ω-3 fatty acid, α-linolenic. In Kenya, linseed is grown in the Rift Valley and Western regions, places which often experience drought. This study was aimed at evaluating the effect of water stress on growth of three linseed cultivars and to establish the extent of drought tolerance in the three cultivars. A greenhouse pot experiment in a completely randomized design was conducted at Jomo Kenyatta University of Agriculture and Technology, Kenya. The pots were well watered until the fourth week when watering was completely withheld to a half of the pots (stressed) while the other half (well watered control) was maintained at 90 % field capacity. Destructive harvesting was done when the stressed pots were at 90, 70, 60, 50, 40 % field capacities and at permanent wilting point. The experiment was replicated thrice and was repeated twice (February-May and August-November 2014). There were no significant differences in production of leaves, plant height, number of tillers and biomass between the three varieties in both seasons. Subjecting the linseed varieties to permanent wilting resulted in reduced production of leaves, growth in height, production of tillers and dry weight by 20-40 %. Decline in all growth parameters begun when 30-80 % of available soil water had been used up. There existed linear relationships between the various evaluated growth parameters. These relationships were not influenced either by the water status of soil or the varieties. Relative water content for the three linseed varieties declined after 25-67 % of available soil water had been used up.

Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components.

Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant) and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity.

Alternatives to the 'water oxidation pathway' of biological ozone formation.

Recent studies have shown that ozone (O3) is endogenously generated in living tissues, where it makes both positive and negative physiological contributions. A pathway for the formation of both O3 and hydrogen peroxide (H2O2) was previously proposed, beginning with the antibody or amino acid-catalyzed oxidation of water by singlet oxygen ((1)O2) to form hydrogen trioxide (H2O3) as a key intermediate. A key pillar of this hypothesis is that some of the H2O2 molecules incorporate water-derived oxygen atoms. However, H2O3 decomposes extremely readily in water to form (1)O2 and water, rather than O3 and H2O2. This article highlights key literature indicating that the oxidation of organic molecules such as the amino acids methionine, tryptophan, histidine, and cysteine by (1)O2 is involved in ozone formation. Based on this, an alternative hypothesis for ozone formation is developed involving a further reaction of singlet oxygen with various oxidized organic intermediates. H2O2 having water-derived oxygen atoms is subsequently formed during ozone decomposition in water by known reactions.

Small reactive carbonyl compounds as tissue lipid oxidation products; and the mechanisms of their formation thereby.

Small reactive carbonyl compounds (RCCs) such as formaldehyde, acetaldehyde, acrolein, crotonaldehyde, glyoxal, methylglyoxal, glycolaldehyde, glycidaldehyde, and 2-butene-1,4-dial are involved in carbonyl and oxidative stress-related physiological disorders. While some evidence indicates that lipid oxidation could be an important source of these compounds in vivo, this has sometimes been doubted because the mechanisms of their formation thereby are poorly understood. Here, representative literature supporting the significant formation of these compounds during lipid oxidation under physiologically relevant conditions are highlighted, and the strengths and weaknesses of previously proposed mechanisms of their formation thereby are considered. In addition, based on the current understanding of lipid oxidation chemistry, some new pathways of their formation are suggested. The suggested pathways also generate 4-hydroxy-2-butenal, a precursor of the carcinogen furan, whose endogenous formation in tissues has hitherto not been seriously considered.

New hypotheses on the pathways of formation of malondialdehyde and isofurans.

Malondialdehyde (MDA) is a mutagenic compound that has been widely used as a biomarker of oxidative stress. However, the nonenzymatic mechanisms of its formation are not well understood. Some lipid oxidation products were previously suggested to be MDA precursors and found to afford MDA heterolytically under acidic conditions. We predict that some of these compounds are not important MDA sources under the autoxidative conditions under which the bulk of MDA should be formed in vivo and that others require further oxidative modifications to generate MDA homolytically. Thus, we outline the likely important pathways of MDA formation in vivo. All these pathways are intense aldehyde producers, generating two other aldehydic products for every MDA molecule formed. Some of the predicted aldehydes are new and may merit further analytical and biological studies. Peracids derived from the aldehydes are proposed to participate in the formation of isofurans (which at high oxygen tensions are excellent markers of oxidative stress) as well as important bioactive epoxides such as leukotoxins. This generates interest in the biological relevance of lipid aldehyde-derived peracids. The suitability of tissue MDA determination methods is discussed based on their likelihood of involving acid-catalyzed artifactual MDA formation.

Different behavior of artemisinin and tetraoxane in the oxidative degradation of phospholipid.

The reaction of trioxane and tetraoxane endoperoxides with unsaturated phospholipid 1 in the presence of Fe(II) was investigated in the absence of oxygen by means of tandem ESI-MS analysis. The spectral analyses for the reaction mixtures showed that artemisinin 2 with a trioxane structure gave no peak except that for the remaining intact phospholipid 1 (m/z 758.9), indicating that there was no structural change to 1. On other hand, the reaction mixture of 1 with tetraoxanes 3 and 4 afforded a number of new peaks (m/z 620-850) that were presumably assigned to oxidative degradation products originating from phospholipid 1. Since this reaction was completely inhibited by the addition of a phenolic antioxidant, the process was considered to involve some free radical species. The newly discovered marked differences in reactivity between the trioxane and the tetraoxanes possibly reflects their different anti-malarial mechanisms, and this reactivity may contribute to the classification of a number of anti-malarial endoperoxides whose mode of action is based on phospholipid oxidation.

A combination of molecular probe-tandem electrospray ionization mass spectrometry: a technique for tracing structural changes in phospholipid hydroperoxides.

An ethyl-labeled phosphatidylcholine hydroperoxide (PC-OOH/Et 2) was synthesized as a molecular probe for naturally occurring PC-OOH 1. Applying the precursor ion scan mode in tandem ESI mass spectrometry at m/z 198, a signal of the PC-OOH/Et 2 alone could be selectively detected even in the presence of a large excess of a complex mixture of phospholipids in the blood. Furthermore, molecular species that formed from PC-OOH/Et 2 by its degradation in the blood were also observed in the same spectrum. Since the molecular probe-and-mass spectrometry-assisted analytical method presented herein requires no separation process by HPLC or TLC and is speedy, requiring less than 1 h, it may be useful in lipid analysis.

Synthesis of novel conjugates of tetraoxane endoperoxide with bis(quaternary ammonium salts).

Novel water-soluble conjugates of 1,2,4,5-tetraoxane bis(quaternary ammonium salts) were synthesized in a relatively stable crystalline form via four steps starting from methyltrioxorhenium-catalyzed endo-peroxidation of ethyl 4-oxocyclohexanecarboxylate with hydrogen peroxide in hexafluoro-2-propanol. The assay for the in vitro toxicity of water-soluble tetraoxanes 5a-5d to malaria parasites indicate that they were inactive against the Plasmodium falciparum FCR-3 strain.