Polyol Compounds Research Articles

Evaluation of Serum and Urine 1,5-Anhydro-D-Glucitol and Myo-Inositol Concentrations in Healthy Dogs

1,5-anhydro-D-glucitol (1,5AG) is a pyranoid polyol compound found in human circulating blood. Myo-inositol (MI) is a stereoisomer of inositol and serves as a precursor of inositol phospholipids. 1,5AG and MI are filtered by the glomerulus and almost completely reabsorbed through the renal tubules. However, under hyperglycemic conditions, reabsorption through the renal tubules is competitively inhibited because the structures of 1,5AG and MI resemble that of glucose. In this study, we investigated the kinetics of serum and urine 1,5AG and MI levels in healthy dogs. We demonstrated that 1,5AG and MI exist in canine serum and urine by gas chromatography-mass spectrometry. Under continuous hyperglycemic conditions, the serum 1,5AG concentration in healthy dogs decreased while the serum MI concentration remained unchanged. Urinary excretion of 1,5AG and MI increased significantly after blood glucose concentrations reached 200 to 220 mg/dl. A significant negative correlation was observed between serum 1,5AG and glucose concentrations during hyperglycemia. However, no significant correlation was observed between serum MI and glucose concentrations. In this study, we demonstrated that serum and urine 1,5AG and MI levels were changed by blood glucose concentrations. The serum 1,5AG concentration was decreased by continuous hyperglycemia. However, the serum MI concentration does not reflect hyperglycemia.

Bioactive secondary metabolites from symbiotic marine dinoflagellates: symbiodinolide and durinskiols

Symbiotic relationships play critical roles in marine ecosystems. Among symbionts, marine dinoflagellates have attracted the attention of natural products chemists, biologists, and ecologists, since they are rich sources of unique bioactive secondary metabolites. The polyol compound symbiodinolide, which was isolated from the symbiotic dinoflagellate Symbiodinium sp., exhibits significant voltage-dependent N-type Ca(2+) channel-opening activity and may serve as a defense substance to prevent digestion of the host animals. Durinskiols are also unique long carbon-chain polyol compounds that were isolated from the dinoflagellate Durinskia sp. We found a selective cleavage reaction of allylic 1,2-diol using an olefin metathesis catalyst, and developed a fluorescent-labeling method for MS/MS analysis to achieve the structural elucidation of huge polyol compounds. This review highlights recent advances in structural and biological studies on symbiodinolide, durinskiols, and related polyol compounds.

Polyol Additives Modulate the In Vitro Stability and Activity of Recombinant Human Phenylalanine Hydroxylase

Phenylketonuria (PKU; OMIM 261600), the most common disorder of amino acid metabolism, is caused by a deficient activity of human phenylalanine hydroxylase (hPAH). Although the dietetic treatment has proven to be effective in preventing the psycho-motor impairment, much effort has been made to develop new therapeutic approaches. Enzyme replacement therapy with hPAH could be regarded as a potential form of PKU treatment if the reported in vitro hPAH instability could be overcome. In this study, we investigated the effect of different polyol compounds, e.g. glycerol, mannitol and PEG-6000 on the in vitro stability of purified hPAH produced in a heterologous prokaryotic expression system. The recombinant human enzyme was stored in the presence of the studied stabilizing agents at different temperatures (4 and -20 degrees C) during a 1-month period. Protein content, degradation products, specific activity, oligomeric profile and conformational characteristics were assessed during storage. The obtained results showed that the use of 50% glycerol or 10% mannitol, at -20 degrees C, protected the enzyme from loss of its enzymatic activity. The determined DeltaG(0) and quenching parameters indicate the occurrence of conformational changes, which may be responsible for the observed increase in catalytic efficiency.

Recent aspects of chemical ecology: Natural toxins, coral communities, and symbiotic relationships

Abstract The discovery of new ecologically active compounds often triggers the development of basic scientific concepts in the field of biological sciences, since such compounds have direct physiological and behavioral effects on other living organisms. We have focused on the identification of natural key compounds that control biologically and physiologically intriguing phenomena. We describe three recent aspects of chemical ecology that we have investigated: natural toxins, coral communities, and symbiotic relationships. Blarina toxin (BLTX) is a lethal mammalian venom that was isolated from the short-tailed shrew. Duck-billed platypus venom shows potent Ca2+ influx in neuroblastoma cells. The venom of the solitary wasp contains arginine kinase-like protein and is used to paralyze its prey to feed its larva. The ecological behaviors of corals are controlled by combinations of small molecules. The polyol compound symbiodinolide may serve as a defense substance for symbiotic dinoflagellates to prevent digestion of their host animals. These compounds reveal the wonder of nature, in both terrestrial and marine ecological systems.

Biologically Active Marine Natural Products

The discovery of new biologically active molecules contributes to the development of basic scientific concepts in the field of biological sciences. These compounds often lead to the development of valuable drugs, and to new pharmacological reagents. They also lead to a better understanding of ecological phenomena. Newly discovered substances can even be responsible for the creation of new scientific fields. Due to the radically different habitats of marine organisms, several notable examples of secondary metabolites from marine organisms have been isolated. Two of the most remarkable properties of these compounds are their structural and physiological diversities. Palytoxin is a polyol compound that shows extreme acute toxicity. Halichondrins are remarkable antitumor macrolides from sponge. Pinnatoxins, potent shellfish poisons, cause food poisoning. The compounds controlling the ecological behaviors of coral reveal to us a wonder of nature. And, the compounds produced by symbiotic microorganisms always inspire us by chemical interests. This paper describes bioorganic studies that are helping to develop new research fields.

Synthesis and Modifications of Polyurethanes for Biomedical Purposes

Polyurethanes are known as a class of polymers with very high ‘hemocompatible‘ properties. In this study polyurethanes were prepared in various compositions and in medical purity without using any solvent, catalyst or additives. For the synthesis of polyurethanes, toluene diisocynate, diphenylmethane diisocynate or hexamethylene diisocynate were used as diisocyanate compounds and polypropylene-ethylene glycol or polypropylene glycol were used as polyol compounds. The surfaces were modified with plasma glow-discharge by using various gas atmospheres and by applying different powers. Some samples were also modified by heparin immobilization to increase the blood compatibility. Chemical structure, mechanical strength, thermal behavior, oxygen permeability, water contact angle values, as well as protein and cell attachment capabilities of the prepared and modified polyurethanes were examined as possible candidates for biomedical applications. Plasma altered the chemistry of the surface, increased hydrophilic character, and caused a decrease in protein adsorption as the applied power was increased. On the other hand, an optimum power value which caused maximum attachment for Vero cells was observed. In-vitro experiments carried out with blood cells, plasma modification caused an increase on cell adhesion while further heparin immobilization resulted with a significant decrease.

Durinskiol A: A Long Carbon‐Chain Polyol Compound from the Symbiotic Dinoflagellate Durinskia sp.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Relative stereochemistries of the ether rings and sugar moieties in durinskiol A

Durinskiol A ( 1) is a long carbon-chain polyol compound with a molecular weight of 2128 mu isolated from the symbiotic dinoflagellate Durinskia sp. The relative stereochemistries of ether rings and sugar moieties in 1 were established based on 2D-NMR analysis and molecular modeling studies. Conformational analysis of the 6,5,6-bis-spiroacetal ring in 1 was also examined by using ab initio methods.

Durinskiol A: a long carbon-chain polyol compound from the symbiotic dinoflagellate Durinskia sp.

A long carbon-chain polyol compound with a molecular weight of 2128 mu, durinskiol A ( 1) was isolated from the cultured symbiotic dinoflagellate Durinskia sp. Its planar structure was elucidated based on 2D-NMR and MS/MS analysis. Durinskiol A ( 1) caused a short body length, abnormal pigment pattern, and pericardiac and yolk-sac edema in zebrafish.

Analysis of Sugars and Sugar Polyols in Atmospheric Aerosols by Chloride Attachment in Liquid Chromatography/Negative Ion Electrospray Mass Spectrometry

Sugars and sugar polyols are relatively abundant groups of water-soluble constituents in atmospheric aerosols. This paper describes a method that uses liquid chromatography-mass spectrometry (LC-MS) to analyze sugars and sugar polyols in atmospheric aerosols, ranging from C3 sugar alcohols to trisaccharides. Postcolumn addition of chloroform in acetonitrile was found to greatly enhance ionization of these compounds by forming chloride adduct ions in the negative-ion mode using electrospray ionization. A gradient elution program starting at 5%:95% H20/acetonitrile and ending at 30%:70% H2O/acetonitrile provides baseline separations of the sugars and sugar polyols on an amino-based carbohydrate column. The detection limits based on quantification of [M + 35Cl]- adduct ions were in the order of 0.1 microM. By eliminating the need for derivatization, this LC-MS based method provides a simpler alternative method to the commonly used and more laborious gas-chromatography based methods. It also has an additional advantage of being able to quantify trisaccharide sugars. The method was applied to analyze 30 ambient samples of fine particulate matter collected at a site away from urban centers in Hong Kong. The sugar compounds positively identified and detected in the ambient samples included four sugar alcohols (glycerol, erythritol, xylitol, and mannitol), three monosacchride sugars (xylose, fructose, and glucose), two disaccharides (sucrose, trehalose), two trisaccharides (melezitose, raffinose), and one anhydrosugar (levoglucosan). The sum of these sugar and sugar polyol compounds ranged from 38 to 1316 ng m(-3), accounting for an average of 1.3% organic carbon mass. Through the use of a principal component analysis of the ambient measurements, the mono- to trisactharide sugars and C3-C5 sugar polyols were identified to be mainly associated with soil/soil microbiota while the anhydrosugar (levoglucosan) was associated with biomass burning.

Boron removal from water by complexation to polyol compounds

Boron is an important micronutrient for plants, animals and humans, although the range between deficiency and excess is narrow. The use of desalinated water and treated wastewater for irrigation may result in excess boron. In aqueous environments (i.e. neutral pH) boron is mainly present as boric acid, which is mostly undissociated and therefore only partially rejected by desalination membranes. Boric acid/borate reacts with neutral polyolic compounds, generating anionic complexes. This work reports on the complexation of boron with mannitol integrated with membrane desalination. The separation of the complex was studied in a wide range of conditions by nanofiltration (NF), and partially by reverse osmosis (RO) membranes. NMR analysis and chemical equilibrium modeling system (Mineql+) were applied to provide a better understanding of experimentally observed rejection patterns. The addition of mannitol in excess formed mainly a 2,2-di-borate ester and some monoborate esters as function of the pH, improving boron rejection by NF up to 90% at pH 9. Mineql+ calculations indicate that reactants concentration has a strong influence on the ionized boron species and therefore on the rejection of boron. Sea water-RO membranes having a much higher basal rejection for boric acid, rejected almost 97% mannitol-complexated boron at pH of 9.

Karatungiols A and B, Two Novel Antimicrobial Polyol Compounds, from the Symbiotic Marine Dinoflagellate Amphidinium sp.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Glucose-Responsive Polyelectrolyte Capsules

Phenylboronic acids are known to form covalent complexes with polyol compounds such as glucose. A novel polyelectrolyte, containing phenylboronic acid as a glucose-sensitive moiety, has been synthesized and used for the fabrication of glucose-sensitive hollow polyelectrolyte capsules using the layer-by-layer technique. The response to glucose was observed as a rather fast dissolution of the capsules when brought into contact with a glucose-containing medium. These polyelectrolyte capsules are the first polyelectrolyte capsules able to respond to a stimulus that can be provided by the human body (i.e., an increase in glucose concentration). Therefore, the concept we present has promising applications in the biomedical field for the controlled delivery of insulin.

Influence of intramolecular hydrogen bonds in the enzyme-catalyzed regioselective acylation of quinic and shikimic acid derivatives

Selective mono-functionalization of 3-epi, 4-epi-, and 5-epi quinic and shikimic acid derivatives has been accomplished by enzymatic acylation with Candida antarctica lipase A (CAL-A). We propose that the selectivity of this lipase is related to both the inherent receptor selectivity and the degree of intramolecular hydrogen bonding in the ligand. Conformational analysis of the hydroxyl protons has been carried out by 1H NMR spectroscopy. We have shown that exchange of the hydroxyl protons by acid catalysis provides a useful method for the detection of intramolecular hydrogen bonds. The interpretation of exchange rates and coupling constants determines the direction of the H-bonds as conditioned by the relative acceptor and donor properties of the hydroxyl groups. The selectivity of the acylation agrees fully with the effectiveness of H-bonding networks in polyol compounds and with the higher reactivity of the equatorial hydroxyl groups.

Karatungiols A and B, two novel antimicrobial polyol compounds, from the symbiotic marine dinoflagellate Amphidinium sp.

Karatungiols A ( 1 ) and B ( 2 ), two novel antimicrobial polyol compounds, were isolated from the cultivated symbiotic marine dinoflagellate Amphidinium sp. Their structures were elucidated based on spectroscopic analysis and degradation reactions. Karatungiols A ( 1 ) and B ( 2 ) consisted of a C69-linear chain with a ketone moiety, 24 or 25 hydroxyl groups, and two tetrahydropyran rings. Karatungiol A ( 1 ) exhibited antifungal activity against Aspergillus niger at 12 μg/disc and antiprotozoan activity against Trichomonas foetus at 1 μg/ml.

Nitrogen and carbon storage in alpine plants

Alpine plants offer unique opportunities to study the processes and economics of nutrient storage. The short alpine growing season forces rapid completion of plant growth cycles, which in turn causes competition between vegetative and reproductive growth sinks during the early part of the growing season. Mobilization of stored nitrogen and carbon reserves facilitates competing sinks and permits successful completion of reproduction before the onset of winter stress. We discuss the theoretical framework for assessing the costs and benefits of nutrient storage in alpine plants in order to lay the foundation for interpretation of observations. A principal point that has emerged from past theoretical treatments is the distinction between reserve storage, defined as storage that occurs with a cost to growth, and resource accumulation, defined as storage that occurs when resource supply exceeds demand, and thus when there is no cost to growth. We then discuss two case studies, one already published and one not yet published, pertaining to the storage and utilization of nitrogen and carbon compounds in alpine plants from Niwot Ridge, Colorado. In the first case, we tested the hypothesis that the seasonal accumulation of amino acids in the rhizome of N-fertilized plants of Bistorta bistortoides provides an advantage to the plant by not imposing a cost to growth at the time of accumulation, but providing a benefit to growth when the accumulated N is remobilized. We show that, as predicted, there is no cost during N accumulation but, not as predicted, there is no benefit to future growth. In the presence of N accumulation, reliance on stored N for growth increases, but reliance on current-season, soil-derived N decreases; thus the utilization of available N in this species is a 'zero sum' process. Inherent meristematic constraints to growth cause negative feedback that limits the utilization of accumulated N and precludes long-term advantages to this form of storage. In the second case study, we discuss new results showing high concentrations of cyclic polyol (cyclitol) compounds in the leaves of many alpine species dominant in the dry fellfield habitat. In Artemisia scopulorum, cyclitols were induced as the growing season progressed, and reached highest concentrations during the dry, late-summer months. Leaf cyclitol concentrations were high in all four species of the Caryophyllaceae that we examined and appeared to be constitutive components of the leaf carbohydrate pool as concentrations were high through the entire growing season. We observed correlations among seedling abundance, seeding survivorship and the presence of high leaf cyclitol concentrations. We propose that the primary function of cyclitols in the leaves of alpine, fellfield herbs is to promote drought tolerance through osmotic protection, and enhance fitness by improving seedling survival. We considered the possibility that cyclitols also function as carbon storage compounds that are remobilized at the end of the growing season and used to support growth the following year. Our observations do not support this hypothesis in the Caryophyllaceae because the requirement for high constitutive concentrations year-after-year prevents long-term advantages of storage and remobilization. However, in A. scopulorum, remobilization of cyclitols following the end of the growing season may provide storage substrates that can be used for growth the following season. From our analysis we conclude that it is difficult to use current theory that is embedded in the economic concept of costs and benefits to interpret observed dynamics in nitrogen and carbon allocation. Future theoretical developments that move away from an abstract foundation embedded in cost-benefit tradeoffs and toward phenotypic integration of source-sink relationships will improve our ability to merge observations and theory.

Bioorganic studies on marine natural products—diverse chemical structures and bioactivities

The discovery of new molecules contributes to the development of basic scientific concepts, leads to valuable drug-oriented compounds, and suggests possible new pharmacological reagents. Newly discovered substances can even be responsible for the creation of new scientific fields. Due to the radically different habitats of marine organisms, several notable examples of secondary metabolites from marine organisms have been isolated. Two of the most remarkable properties of these compounds are their structural and physiological diversities. These bioactive compounds are candidates for drugs or biological probes for physiological studies. Palytoxin is a polyol compound that shows extreme acute toxicity. Halichondrins are remarkable antitumor macrolides from sponge. Pinnatoxins, potent shellfish poisons, cause food poisoning. This paper describes bioorganic studies on such newly discovered wonders of nature. Several bioactive marine alkaloids and important substances involved in dynamic ecological systems are also described.

The effect of polyol compounds on the thermostability of penicillin G acylase from a mutant of Escherichia coli ATCC 11105

The effects of the 15 polyol compounds on the thermostability of penicillin G acylase (PGA) from a mutant of Escherichia coli ATCC 11105 were investigated. PGA solutions containing glucose, sucrose, mannose, adonitol, sorbitol or xylitol at 1 m concentration showed an initial activity rate (IAR) higher than 3. The IAR values of these six sugars at 50°C increased with their concentrations in PGA solution. The investigations on half-life times and stabilization factor (SF) values of PGA at 45 and 50°C, in the presence of these compounds, showed a tendency for the half-life and SF of the enzyme, at 50°C, to increase with the OH/C ratios of polyol compounds. Sucrose and glucose were the only two compounds having higher SF values at 50°C than at 45°C. Sucrose showed almost twice the half-life of glucose and was selected as the best stabiliser of PGA activity against thermal inactivation. PGA showed almost the state of pH and temperature activity profiles in both presence and absence of sucrose. K m and V m values decreased with the increasing sucrose concentrations, with a greater decrease in K m values.

The Effect of Polyol Compounds on the Thermostability of Penicillin G Acylase from a Mutant of Escherichia coli ATCC 11105

The Effect of Polyol Compounds on the Thermostability of Penicillin G Acylase from a Mutant of Escherichia coli ATCC 11105

Boronate-Containing Polymer as Novel Mitogen for Lymphocytes

A novel water-soluble polymer (poly(AAm-co-PBA)) was synthesized by radical copolymerization of 3-acrylamidophenylboronic acid with acrylamide and evaluated as synthetic mitogen of lymphocytes. Boronic acid was introduced in the polymer as recognition site of sugar residues existing on the plasma membrane surface of lymphocyte, since it makes a covalent bonding with polyol compounds including sugars. Obvious increase in [ 3H]thymidine incorporation of lymphocytes was observed when murine spleen lymphocytes were cultured with poly(AAm-co-PBA), while little proliferative response of lymphocytes was observed in the presence of the homopolymer of acrylamide, the polymer without boronic acid moiety. This suggests that proliferation of lymphocytes was induced through the binding of phenylboronic acid moiety in poly(AAm-co-PBA) with glycoproteins existing on the plasma membrane surface of lymphocytes. Further, poly(AAm-co-PBA) was found to induce even the proliferation of B cell-depleted population of lymphocytes, suggesting T cell stimulation by this boronate-containing polymer.