ABSTRACT
Concomitant with nephrotic syndrome and multicentric castleman's disease (MCD) has only been described in a limited number of small studies and case reports. Among those, none confirmed the renal pathology prior to the onset of MCD, and none of the cases had a history of nephrotic syndrome. A 76 year-old Japanese man visited a nephrologist because of incident nephrotic syndrome. He had previously experienced three episodes of nephrotic syndrome, the last one 13 years ago, and had been diagnosed with membranous nephropathy by renal biopsy. Apart from these previous episodes, he also suffered from systemic lymphadenopathy, anemia, elevated C-reactive protein, polyclonal hypergammopathy, and elevated interleukin (IL)-6. An inguinal lymph node biopsy revealed CD138-positive plasma cells in the interfollicular region. Based on these findings, MCD was diagnosed. Renal biopsy indicated primary membranous nephropathy with spike lesions and bubbling in the basement membranes and deposition of immunoglobulin (Ig) G, IgA, IgM, and phospholipase A2 receptor along the glomerular basement membrane. Corticosteroid monotherapy successfully reduced the edema, proteinuria, and IL-6, but hypoalbuminemia was not sufficiently improved due to castleman's disease and remission of the nephrotic syndrome was not achieved. Later, tocilizumab was administered for remission induction in another facility. To the best of our knowledge, this represents the first report of Castleman's disease with previously diagnosed membranous nephropathy. This case does not provide a causal mechanism for the pathophysiology, but it may be worth suggesting possible involvement of MCD as a trigger for recurrence of membranous nephropathy.
ABSTRACT
Photoluminescent coordination nanosheets (CONASHs) comprising three-way terpyridine (tpy) ligands and zinc(II) ions are created by allowing the two constitutive components to react with each other at a liquid/liquid interface. Taking advantage of bottom-up CONASHs, or flexibility in organic ligand design and coordination modes, we demonstrate the diversity of the tpy-zinc(II) CONASH in structures and photofunctions. A combination of 1,3,5-tris[4-(4'-2,2':6',2â³-terpyridyl)phenyl]benzene (1) and Zn(BF4)2 affords a cationic CONASH featuring the bis(tpy)Zn complex motif (1-Zn), while substitution of the zinc source with ZnSO4 realizes a charge-neutral CONASH with the [Zn2(µ-O2SO2)2(tpy)2] motif [1-Zn2(SO4)2]. The difference stems from the use of noncoordinating (BF4-) or coordinating and bridging (SO42-) anions. The change in the coordination mode alters the luminescence (480 nm blue in 1-Zn; 552 nm yellow in 1-Zn2(SO4)2). The photophysical property also differs in that 1-Zn2(SO4)2 shows solvatoluminochromism, whereas 1-Zn does not. Photoluminescence is also modulated by the tpy ligand structure. 2-Zn contains triarylamine-centered terpyridine ligand 2 and features the bis(tpy)Zn motif; its emission is substantially red-shifted (590 nm orange) compared with that of 1-Zn. CONASHs 1-Zn and 2-Zn possess cationic nanosheet frameworks with counteranions (BF4-), and thereby feature anion exchange capacities. Indeed, anionic xanthene dyes were taken up by these nanosheets, which undergo quasi-quantitative exciton migration from the host CONASH. This series of studies shows tpy-zinc(II) CONASHs as promising potential photofunctional nanomaterials.
ABSTRACT
The Pictet-Spengler reaction between tryptamine and aldehydes was catalyzed by Dowex 50W-X4 acidic ion-exchange resin. The products were obtained from the resin in high purity by 'catch and release' without the need for separate chromatographic purification.
Subject(s)
Chemical Fractionation/methods , Ion Exchange Resins/chemistry , Aldehydes/chemistry , Catalysis , Hydrogen-Ion Concentration , Tryptamines/chemistryABSTRACT
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.
Subject(s)
Antimalarials/chemistry , Artemisinins/chemistry , Phosphatidylcholines/chemistry , Tetraoxanes/chemistry , Antimalarials/pharmacology , Iron/chemistry , Lipid Peroxidation , Phosphatidylcholines/analysis , Prostaglandin Endoperoxides, Synthetic/chemistry , Spectrometry, Mass, Electrospray Ionization , Tetraoxanes/pharmacologyABSTRACT
Phospholipase D (PLD) is a biocatalyst in the synthesis of bioactive compounds and a key enzyme in a variety of biological signal transductions. A combination of unnatural phosphatidyl acceptor, N,N,N-triethyl-N-2-hydroxyethylammonium bromide 6, as a substrate for PLD, and tandem electrospray ionization mass spectrometry (ESI MS) was found to provide information as to whether a given phospholipid serves as a substrate for the PLD-catalyzed reaction. Thus 2-(13'-hydroperoxy-octadecadienoyl)-1-palmitoylglycerophosphocholine 1, and its degradation products 2-(13'-oxo-octadecadienoyl)-1-palmitoylglycerophosphocholine 9 and 2-(13'-hydroxy-octadecadienoyl)-1-palmitoylglycerophosphocholine 11, in a mixture were found to be a substrate of the PLD-catalyzed transphosphatidylation. The sensitivity of this method was exemplified by the observation that PLD activity in cabbage leaves was detected using a small amount of crude crushed leaves with little pretreatment. This simple method can be used in screening for PLD activity and searching for inhibitors of the enzyme from various natural sources.
Subject(s)
Choline/analogs & derivatives , Phospholipase D/metabolism , Quaternary Ammonium Compounds/metabolism , Biocatalysis , Brassica/enzymology , Choline/metabolism , Plant Leaves/enzymology , Spectrometry, Mass, Electrospray Ionization , Tandem Mass SpectrometryABSTRACT
Death-feigning, also called tonic immobility, is found in a number of animal species across vertebrate and invertebrate taxa. To date, five hypotheses have been proposed for the adaptive significance of tonic immobility. These are that tonic immobility is effective for prey because (i) avoiding dead prey is safer for predators, (ii) immobility plays a role in physical defence, (iii) immobility plays a role in concealment and/or background matching, (iv) predators lose interest in unmoving prey, and (v) the characteristic immobilization posture signals a bad taste to predators. The fourth and fifth hypotheses have been considered suitable explanations for tonic immobility of the red flour beetle against its predator, the jumping spider. In the present study, we used chemical analyses of secretions by the red flour beetles under attack by the jumping spider to reject the fifth hypothesis for this system. More importantly, we tested a selfish-prey hypothesis for the adaptive significance of death-feigning as an anti-predator strategy, in which individuals adopting tonic immobility survive by sacrificing neighbours. Findings showed that survival rates of feigners were higher when in the presence of non-feigners or prey of a different species, compared to when alone, thus confirming our selfish-prey hypothesis. In summary, our results suggest that immobility following a spider attack is selfish; death-feigning prey increase their probability of survival at the expense of more mobile neighbours.
Subject(s)
Coleoptera/physiology , Immobility Response, Tonic/physiology , Spiders/physiology , Animals , Benzoquinones/metabolism , Predatory BehaviorABSTRACT
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.
Subject(s)
Molecular Probes/chemistry , Phosphatidylcholines/chemistry , Humans , Molecular Probes/chemical synthesis , Phosphatidylcholines/blood , Phosphatidylcholines/metabolism , Spectrometry, Mass, Electrospray Ionization , Tandem Mass SpectrometryABSTRACT
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.
Subject(s)
Tetraoxanes/chemical synthesis , Animals , Crystallization , Hydrogen Peroxide , Plasmodium falciparum/drug effects , Quaternary Ammonium Compounds/chemistry , Solubility , Tetraoxanes/pharmacologyABSTRACT
Maltosides of butanol, octanol, and lauryl alcohol were found for the first time to serve as substrates for cyclomaltodextrin glucanotransferase (CGTase), and glycosyl residue was transfered from dextrin to the substrate affording novel maltosides with 3-4 glucose units.
Subject(s)
Alcohols/chemistry , Biocatalysis , Dextrins/metabolism , Geobacillus stearothermophilus/enzymology , Glucosides/chemistry , Glucosides/metabolism , Glucosyltransferases/metabolism , GlycosylationABSTRACT
We synthesized all of the monomethoxycoumarins, 5-alkoxycoumarins and their derivatives, and investigated their nematicidal activity against the phytopathogenic nematode, Bursaphelenchus xylophilus. Among the compounds, 5-ethoxycoumarin showed the highest nematicidal activity. Furthermore, 5-ethoxycoumarin was comparatively harmless against both the brine shrimps, Artemia salina, and the Japanese killifish, Oryzias latipes.
Subject(s)
Antinematodal Agents/chemical synthesis , Chemistry, Pharmaceutical/methods , Animals , Antinematodal Agents/pharmacology , Artemia , Biological Assay , Coumarins/chemistry , Coumarins/pharmacology , Drug Design , Hydrolysis , Models, Chemical , Nematoda , Oryzias , Structure-Activity RelationshipABSTRACT
Five ingenane compounds, 1-5, kansuinins A and B, isolated from Euphorbia kansui, and their derivatives 7 and 9 were tested for termiticidal activity against the Japanese termite, Reticulitermes speratus. At 72 hours after treatment, the ingenane compounds 1 to 5 caused 100% mortality in R. speratus at 50, 25 and 12.5 microg/disk, respectively, except for compound 1, which gave a mortality rate of (93.06 +/- 5.56)% at 12.5 microg/disk. At 36, 48 and 60 hours after treatment, compounds 1 to 5 showed more termiticidal activity than kansuinins A and B and their derivatives. The kansuinins showed no or only slight activity against termites in the filter paper bioassay under the conditions tested compared with a solvent control.
Subject(s)
Diterpenes/toxicity , Euphorbia/chemistry , Insecticides/toxicity , Isoptera/drug effects , Plant Roots/chemistry , Animals , Diterpenes/chemistry , Diterpenes/isolation & purification , Insecticides/chemistry , Insecticides/isolation & purification , Magnetic Resonance Spectroscopy , Models, MolecularABSTRACT
Under the bioassay-guided method, two diterpenes, 3-O-(2",3"-dimethylbutanoyl)-13-O-dodecanoylingenol (1) and 3-O-(2",3"-dimethylbutanoyl)-13-O-decanoylingenol (2) isolated from Euphorbia kansui, showed a pronounced antinematodal activity against the nematode Bursaphelenchus xylophilus at the same minimum effective dose (MED) of 5 microg per cotton ball and still displayed antinematodal activity at a dose of 2.5 microg per cotton ball. Compounds 3-6 were obtained, and the structure of the new compound 6 was elucidated based on 1D- and 2D-NMR analyses and physicochemical data. Preliminary structure-biological activity relationships of ingenane-type compounds were deduced.
Subject(s)
Antinematodal Agents/toxicity , Diterpenes/toxicity , Euphorbia/chemistry , Nematoda/drug effects , Plant Roots/chemistry , Wood/parasitology , Animals , Diterpenes/isolation & purification , Models, Molecular , Pinus/parasitologyABSTRACT
Novel fatty acyl and phospholipid derivatives of pyrrole polyamide were synthesized. Their cytotoxicity against a cancer cell line of MT-4 cells and those infected by human immunodeficiency virus (HIV) was examined. Although no anti-HIV activity was found, their cytotoxicitty against the cancer cells was significantly enhanced by introducing a lipophilic group into the pyrrole polyamide.
Subject(s)
Anti-HIV Agents/chemical synthesis , Anti-HIV Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/pharmacology , Lipids/chemical synthesis , Lipids/pharmacology , Nylons/chemical synthesis , Nylons/pharmacology , Pyrroles/chemical synthesis , Pyrroles/pharmacology , Cell Line, Tumor , Drug Screening Assays, Antitumor , Fatty Acids/chemistry , Humans , Indicators and Reagents , Magnetic Resonance Spectroscopy , Phospholipids/chemistryABSTRACT
Three compounds, 20-O-acetyl-[3-O-(2'E,4'Z)-decadienoyl]-ingenol (1), 20-O-acetyl-[5-O-(2'E,4'Z)-decadienoyl]-ingenol (2) and 3-O-(2'E,4'Z)-decadienoylingenol (3), were isolated from Euphorbia kansui under the bioassay-guided method. Each compound showed the same antinematodal activity against the nematode, Bursaphelenchus xylophilus, at a minimum effective dose (MED) of 5 microg/cotton ball.
Subject(s)
Antinematodal Agents/isolation & purification , Antinematodal Agents/pharmacology , Diterpenes/isolation & purification , Diterpenes/pharmacology , Euphorbia/chemistry , Chromatography, Thin Layer , Diterpenes/chemical synthesis , Indicators and Reagents , Magnetic Resonance Spectroscopy , Models, Molecular , Plant Roots/chemistry , Spectrometry, Mass, Electrospray Ionization , Spectrometry, Mass, Fast Atom Bombardment , Spectrophotometry, Infrared , Spectrophotometry, UltravioletABSTRACT
Sucrose monolauroyl esters were found to serve as substrates for cyclodextrin glucanotransferase (CGTase)-catalyzed transglucosidation reactions, affording new sucrose esters that have an additional 1-3 glucose residues on the pyranose ring of the sucrose moiety in the ester.
Subject(s)
Glucosyltransferases/chemistry , Sucrose/analogs & derivatives , Glucose/chemistry , Sucrose/chemistryABSTRACT
By using a new bioassay-guided method, 2-hydroxy-4-methoxybenzaldehyde isolated from the root bark of Periploca sepium, a traditional Chinese medicine, showed repellent activity against the olive weevil (Dyscerus perforatus) at 62.5, 125, 250 and 500 microg/disc, respectively. In addition, it also exhibited antinematodal activity against Bursaphelenchus xylophilus at a minimum effective dose of 200 microg/ball. The three related compounds obtained were also evaluated for the above-mentioned bioactivities.
Subject(s)
Insect Repellents/chemistry , Medicine, Chinese Traditional , Periploca/chemistry , Animals , Biological Assay/instrumentation , Biological Assay/methods , China , Insect Repellents/isolation & purification , Insect Repellents/pharmacology , Nematoda/drug effects , Plant Oils/chemistry , Plant Oils/isolation & purification , Plant Oils/pharmacology , Structure-Activity Relationship , Weevils/drug effectsABSTRACT
Derivatives of quinine with fatty acids including polyunsaturated fatty acids were prepared. They showed moderate antimalarial activity as compared with quinine itself using Plasmodium falciparum. The activities were not dependent on whether the fatty acyl group was saturated or unsaturated. On the other hand, the derivatives showed significantly higher cytotoxicity against a mammary tumor cell line FM3A than quinine itself. Calculating from these data, an acetyl derivative of quinine with the shortest acyl group was found to give the highest selectivity.
Subject(s)
Antimalarials/chemical synthesis , Antineoplastic Agents/chemical synthesis , Fatty Acids/chemistry , Quinine/analogs & derivatives , Quinine/pharmacology , Animals , Antimalarials/pharmacology , Antineoplastic Agents/pharmacology , Breast Neoplasms/drug therapy , Breast Neoplasms/pathology , Cell Line, Tumor , Female , Mice , Plasmodium falciparum/drug effects , Quinine/chemical synthesis , Structure-Activity RelationshipABSTRACT
Several 3-alkylphenols including 3-undecylphenol, which was isolated from a Sumatran rainforest plant, were synthesized to investigate their antinematodal activity against the phytopathogenic nematodes, Bursapherencus xylophilus. A three-step synthesis involving the treatment of 2-cyclohexen-1-one with the Grignard reagent, oxidation of the resulting 1-alkyl-2-cyclohexen-1-ol and subsequent aromatization of 3-alkyl-2-cyclohexen-1-one successfully afforded such phenols. Among the 3-alkylphenols, 3-nonylphenol showed the highest activity, while 3-decylphenol and 3-undecylphenol also showed high activity.
Subject(s)
Antinematodal Agents/pharmacology , Phenols/chemical synthesis , Phenols/pharmacology , Animals , Antinematodal Agents/chemical synthesis , Dose-Response Relationship, Drug , Indicators and Reagents , Magnetic Resonance Spectroscopy , Nematoda , Spectrometry, Mass, Electrospray Ionization , Structure-Activity RelationshipABSTRACT
Phosphatidylcholines (PCs) having an acyl chain with a 2,4-dienal terminal are expected to be important bioactive compounds formed during lipid peroxidation in vivo. However, they have not been isolated from biological tissues. Here we used electrospray mass spectroscopy to investigate whether a high autoxidative instability may contribute to the difficulty in detecting one such compound, 13-oxo-9,11-tridecadienoyl PC (OTDA-PC, 1). Although we found that pure, synthetic OTDA-PC was very stable, OTDA-PC formed during the decomposition of a PC bearing the 13-hydroperoxide of alpha-linolenic acid (PC-LNA-OOH, 2) was readily converted (i) anaerobically to its corresponding acid PC, 13-carboxy-9,11-tridecadienoyl PC, 3; (ii) aerobically to other bioactive aldehyde (or acid) PC species that have been detected in atherosclerotic tissues. We attribute the high oxidative instability of OTDA-PC to a high vulnerability of its carbonyl hydrogen [H-C(=O)R] to abstraction by lipid-derived radicals, and propose mechanisms for its conversion to the other oxidised PC species (vide supra).
Subject(s)
Alkadienes/chemistry , Fatty Acids, Unsaturated/chemistry , Liposomes/chemistry , Phosphatidylcholines/chemistry , Aerobiosis , Aldehydes/chemistry , Anaerobiosis , Free Radicals/chemistry , Lipid Peroxidation , Models, Chemical , Oxidation-Reduction , Spectrometry, Mass, Electrospray Ionization , alpha-Linolenic Acid/chemistryABSTRACT
Beta-sitosteryl-D-glucoside and oleuropein isolated from the olive tree (Olea europaea) and their hydrolysed derivatives were tested by a feeding stimulative activity bioassay using the olive weevil (Dyscerus perforatus). Although the steroidal glucoside showed potent feeding stimulative activity, the activity of the aglycone (beta-sitosterol) was significantly lower than that of the glucoside. On the other hand, the difference in the activity between oleuropein, a secoiridoid glucoside, and the hydrolysed derivatives was not significant.