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Biomedical subjects

C J Barrow

Publications and source records attributed to C J Barrow.

At least 37 records · Page 2Linked to original sources

Familial prion disease mutation alters the secondary structure of recombinant mouse prion protein: implications for the mechanism of prion formation.

A considerable body of data supports the model that the infectious agent (called a prion) which causes the transmissible spongiform encephalopathies is a replicating polypeptide devoid of nucleic acid. Prions are believed to propagate by changing the conformation of the normal cellular prion protein (PrPc) into an infectious isoform without altering the primary sequence. Proteins equivalent to the mature form of the wild-type mouse prion protein (residues 23-231) or with a mutation equivalent to that associated with Gerstmann-Straüssler-Scheinker disease (proline to leucine at codon 102 in human; 101 in mouse) were expressed in E. coli. The mutation did not alter the relative proteinase K susceptibility properties of the mouse prion proteins. The wild-type and mutant proteins were analyzed by circular dichroism under different pH and temperature conditions. The mutation was associated with a decrease in alpha-helical content, while the beta-sheet content of the two proteins was unchanged. This suggests the mutation, while altering the secondary structure of PrP, is not sufficient to induce proteinase K resistance and could therefore represent an intermediate isoform along the pathway toward prion formation.

Amino Acid Substitution↗

On-line high-performance liquid chromatography/mass spectrometric investigation of amyloid-beta peptide variants found in Alzheimer's disease.

Abeta peptides are the major components of amyloid deposits in Alzheimer's disease. The presence of N-terminally truncated Abeta variants in amyloid may be a critical factor in Alzheimer's disease pathogenesis. These Abeta variants are less soluble and more amyloidogenic than full-length Abeta, making their separation, purification and identification difficult. High-performance liquid chromatography (HPLC) at elevated temperatures, coupled to electrospray ionization (ES) mass spectrometry (MS), enables rapid separation and identification of N-terminally truncated Abeta variants. This methodology provides a potential tool for exploring the importance of these Abeta variants in both the pathogenesis and diagnosis of Alzheimer's disease.

Alzheimer Disease↗

Synthesis and secondary structural studies of penta(acetyl-Hmb)A beta(1-40).

The Fmoc solid phase synthesis of A beta(1-40), a strongly aggregating peptide found in Alzheimer's disease brain, was performed using 2-hydroxy-4-methoxybenzyl (Hmb) backbone amide protection. Hmb-Gly residues were incorporated using N(alpha)-Fmoc-Hmb-Gly-OH rather than N,O-bisFmoc-Hmb-Gly-OPfp. Amino acid acylation of the sterically hindered Hmb-amino acids was monitored using 'semi-on-line' MALDI-TOF-MS in a novel application of this technique which significantly simplified the successful incorporation of these residues. Standard coupling conditions in N,N-dimethylformamide (DMF) were used throughout the synthesis. Comparative structural studies of acetyl-Hmb-protected and native A beta(1-40) were performed to investigate the structural basis of Hmb-mediated disaggregation. The incorporation of backbone amide protection was observed by circular dichroism spectroscopy and gel electrophoresis to strongly affect the solution structure of A beta(1-40). Despite the reported structure-breaking activity of Hmb groups, penta(acetyl-Hmb)A beta(1-40) was found to adopt both alpha-helix and intermolecular beta-sheet conformations. In 100% TFE a mixed alpha-helix/random coil structure was formed by the protected peptide indicating reduced alpha-helical propensity relative to A beta(1-40). The protected peptide formed beta-sheet structures in aqueous buffer. Gel electrophoresis indicated that, unlike native A beta(1-40), penta(acetyl-Hmb)A beta(1-40) did not form large aggregate species.

Acylation↗

The hydrophobic core sequence modulates the neurotoxic and secondary structure properties of the prion peptide 106-126.

The neurodegeneration seen in spongiform encephalopathies is believed to be mediated by protease-resistant forms of the prion protein (PrP). A peptide encompassing residues 106-126 of human PrP has been shown to be neurotoxic in vitro. The neurotoxicity of PrP106-126 appears to be dependent upon its adoption of an aggregated fibril structure. To examine the role of the hydrophobic core, AGAAAAGA, on PrP106-126 toxicity, we performed structure-activity analyses by substituting two or more hydrophobic residues for the hydrophilic serine residue to decrease its hydrophobicity. A peptide with a deleted alanine was also synthesized. We found all the peptides except the deletion mutant were no longer toxic on mouse cerebellar neuronal cultures. Circular dichroism analysis showed that the nontoxic PrP peptides had a marked decrease in beta-sheet structure. In addition, the mutants had alterations in aggregability as measured by turbidity, Congo red binding, and fibril staining using electron microscopy. These data show that the hydrophobic core sequence is important for PrP106-126 toxicity probably by influencing its assembly into a neurotoxic structure. The hydrophobic sequence may similarly affect aggregation and toxicity observed in prion diseases.

Alanine↗

Isolation and partial structure determination of a clonidine-displacing substance from bovine lung and brain.

A large scale extraction and isolation method was developed for the purification of clonidine-displacing substance (CDS) activity from bovine lung or brain. This optimised method used direct freeze drying of tissue, hexane removal of lipids, and methanol extraction of CDS activity. Using a bioassay directed isolation strategy a new CDS compound was purified from an extract of bovine lung. The isolation strategy involved subsequent steps of flash C-18 chromatography, ion exchange, size exclusion, and C-18 HPLC. An HPLC detection method was developed and applied to show that the new CDS is present in both lung and brain tissue. Spectroscopic data for this new CDS indicates that it is related to guanosine, but is not noradrenaline, adrenaline, histamine, agmatine, guanosine, GMP, GDP or GTP.

Adrenergic alpha-Agonists↗

Antimycins, inhibitors of ATP-citrate lyase, from a Streptomyces sp.

A related group of compounds belonging to the antimycin class of antibiotics was found in culture broth produced by a Streptomyces species. The group includes known antimycins A1, A2, A3 and A4, and new antimycins A7 and A8. These compounds inhibit ATP-citrate lyase with Ki values of 4 to 60 microM against the substrate magnesium citrate. The structures of the new antimycins were determined by spectroscopic analyses.

ATP Citrate (pro-S)-Lyase↗

The role of inferior parietal cortex and fornix in route following and topographic orientation in cynomolgus monkeys.

The effects of inferior parietal cortex lesions (Area 7a/PG) and bilateral transection of the fornix were compared within a single species (cynomolgus monkeys) and using a single paradigm of route running in a traditional (fixed entry and exit) whole-body maze. Experiment 1 showed that Area 7a/PG but not fornix lesions impaired post-operative retention of route running. Experiment 2 assessed the contribution of visual cues and proprioceptive/kinaesthetic guidance to route running and showed that in non-lesioned monkeys route running was influenced to varying degrees by proprioceptive guidance, visual extra-maze room cues and visual maze stimuli. Post-operative assessment of maze performance, including error patterns, retraining and misreaching (Experiment 1), suggested that monkeys in the Parietal Group were not topographically disoriented and did not have a spatial long-term memory deficit, but it was their difficulty responding to local spatial cues which initially impaired route running. Investigation of cue use (Experiment 2) also showed the sensitivity of the Parietal Group to local spatial cues; they were significantly impaired on entry through a new start position when the relationship between maze stimuli and extra-maze cues was changed. The Fornix Group showed no retrograde long-term memory deficit for route-running (Experiment 1). However, in Experiment 2, where a new goal position was learnt, the Fornix Group did show an anterograde memory deficit.

Animals↗

Agmatine: an endogenous clonidine-displacing substance in the brain.

Clonidine, an antihypertensive drug, binds to alpha 2-adrenergic and imidazoline receptors. The endogenous ligand for imidazoline receptors may be a clonidine-displacing substance, a small molecule isolated from bovine brain. This clonidine-displacing substance was purified and determined by mass spectroscopy to be agmatine (decarboxylated arginine), heretofore not detected in brain. Agmatine binds to alpha 2-adrenergic and imidazoline receptors and stimulates release of catecholamines from adrenal chromaffin cells. Its biosynthetic enzyme, arginine decarboxylase, is present in brain. Agmatine, locally synthesized, is an endogenous agonist at imidazoline receptors, a noncatecholamine ligand at alpha 2-adrenergic receptors and may act as a neurotransmitter.

Adrenal Medulla↗

Structure determination, pharmacological evaluation, and structure-activity studies of a new cyclic peptide substance P antagonist containing the new amino acid 3-prenyl-beta-hydroxytyrosine, isolated from Aspergillus flavipes.

Two novel cyclic heptapeptides, peptides 1a and 1c, were isolated from an Aspergillus flavipes culture, originally isolated from soil, and their structures established by chemical and spectroscopic evidence. Peptide 1a contains a new amino acid, 3-prenyl-beta-hydroxytyrosine, and is a competitive antagonist to substance P at the human NK1 receptor, with an inhibitor affinity constant (Ki) of 8 +/- 4 microM. Methylation of 1a gave the monomethyl derivative 1b, which is a more potent competitive antagonist, with a Ki of 0.12 +/- 0.03 microM at the human NK1 receptor. Herein we report the structure determinations of 1a and 1c, and some structure-activity results. Several analogs of 1a were prepared by derivatization and synthesis. Structure-activity results for these analogs confirmed that the 3-prenyl-beta-hydroxytyrosine moiety is critical for the biological potency of 1a and 1b.

Amino Acid Sequence↗

Spiroquinazoline, a novel substance P inhibitor with a new carbon skeleton, isolated from Aspergillus flavipes.

A novel substance P inhibitor, spiroquinazoline [1], was isolated from the fungus Aspergillus flavipes, which was originally obtained from soil. The structure of 1 was determined by analysis of spectroscopic data and 1 was shown to contain a new carbon skeleton containing a spiro-carbon center. Also isolated from the same culture extract were the new natural product, benzodiazepiedione [3], and the known compounds, acyl aszonalenin [4], N-benzoyl-L-phenylalaninol, and seven diketopiperazines.

Antineoplastic Agents↗

1'-(2-Phenyl-ethylene)-ditryptophenaline, a new dimeric diketopiperazine from Aspergillus flavus.

A new diketopiperazine dimer, 1'-(2-phenyl-ethylene)-ditryptophenaline [1], was isolated together with ditryptophenaline [2] from the fungus Aspergillus flavus. The structure of 1 was determined by analysis of spectroscopic data. In contrast to the structurally related substance-P antagonist WIN 64821 [3], both 1 and 2 are weak substance-P inhibitors, indicating that stereochemistry at the position of dimerization is an important determinant of biological potency for these molecules.

Aspergillus flavus↗

Cucurbitacins, cell adhesion inhibitors from Conobea scoparioides.

In the course of screening natural products for antagonists of CD18-mediated cell adhesion, an extract with inhibitory activity was identified from the stem and leaves of Conobea scoparioides. Bioassay-guided fractionation led to a pure compound, identified by spectroscopy as cucurbitacin E [1]. Although many biological activities have been reported for the cucurbitacins, this is the first report of cell adhesion inhibition. Furthermore, closely related cucurbitacin analogues had different potencies, pointing to substructural features that are important for the activity.

Actins↗

WIN 66306, a new neurokinin antagonist produced by an Aspergillus species: fermentation, isolation and physico-chemical properties.

WIN 66306 (1a), a cyclic peptide containing a novel amino acid, was isolated as a neurokinin antagonist from an Aspergillus species, labelled SC230. Conditions that maximized the production of 1a were developed, leading also to production of the related compound WIN 68577 (2) and rosellichalasin (3). Both 2 and 3 were more active in the rat NK1 than in the human NK1 receptor binding assay, while 1a was more active at the human receptor with an inhibitor affinity constant of 7 microM.

Amino Acid Sequence↗

WIN 64821, a novel neurokinin antagonist produced by an Aspergillus sp. I. Fermentation and isolation.

WIN 64821, a nonpeptide neurokinin antagonist, was isolated from a strain of Aspergillus sp., SC319. The compound was produced in different fermentation media with greatest yields observed when the culture was grown in a synthetic medium supplemented with L-tryptophan and L-phenylalanine. After 6 days fermentation, yields greater than 600 mg/liter were obtained. Two analogs of WIN 64821 were also identified in the culture extracts and subsequently tested for biological activity. WIN 64821 was the most potent compound isolated from this culture and exhibited activity as a substance P-binding inhibitor with submicromolar potency against the human neurokinin 1 receptor.

Aspergillus↗

WIN 64821, a novel neurokinin antagonist produced by an Aspergillus sp. II. Biological activity.

WIN 64821, a secondary metabolite produced by Aspergillus sp. (ATCC 74177) was found to inhibit radiolabeled substance P (SP) binding in a variety of tissues, including those of human origin. This compound inhibited, in a competitive manner, the binding of SP with Ki values ranging from 0.24 microM in human astrocytoma U-373 MG cells to 7.89 microM in rat submaxillary membranes. Additionally, WIN 64821 was found to inhibit 125I-NKA binding to the NK2 receptor in human tissue at a concentration equivalent to its NK1 activity (0.26 microM). The inhibitory activity of WIN 64821 against an NK3 selective ligand, 3H-senktide, was found to be much weaker (Ki = 15.2 microM). WIN 64821 was also evaluated in NK1 functional assays and was found to be a competitive antagonist of SP-induced contractility in the guinea pig ileum (pA2 = 6.6) as well as an inhibitor of SP-induced 45Ca2+ efflux from human astrocytoma U-373 MG cells (IC50 = 0.6 microM). In a rat vas deferens model, WIN 64821 inhibited eledoisin-induced contractility with an IC50 of 3.4 microM indicating functional antagonism at the NK2 receptor. The data presented in this study provide biochemical, pharmacological and functional evidence supporting WIN 64821 as a competitive neurokinin antagonist.

Amino Acid Sequence↗

WIN 64821, a novel neurokinin antagonist produced by an Aspergillus sp. III. Biosynthetic analogs.

WIN 64821 (1) is a substance P (SP) antagonist isolated from a fungal culture (Aspergillus sp., SC319). It is a symmetrical dimer biosynthesized from four aromatic amino acid molecules: each equivalent half of the dimer is constructed from one molecule of phenylalanine (Phe) and one molecule of tryptophan (Trp). Feeding analogs of Phe, Trp, and other amino acids to intact cells of SC319 has yielded 36 biosynthetic analogs of WIN 64821. The analogs fall into three categories: substitutions on the indoline ring, substitutions on the Phe-derived phenyl ring, and replacement of the phenyl ring by an aliphatic group. In addition, these directed biosynthesis experiments generated asymmetrical dimers (derived from three amino acids) and, often, symmetrical dimers (derived from two amino acids). The relative SP binding affinities of several analogs suggest involvement of both the indoline and phenyl moieties in SP receptor binding.

Aspergillus↗

Benzomalvins, new substance P inhibitors from a Penicillium sp.

In the course of screening microbial broths for neurokinin receptor antagonists, a series of new benzodiazepines, benzomalvins A (1), B (2) and C (3), has been isolated from the culture broth of a fungus identified as a Penicillium sp. Benzomalvin A (1) showed inhibitory activity against substance P with Ki values of 12, 42 and 43 microM at the guinea pig, rat and human neurokinin NK1 receptors, respectively. Benzomalvins B (2) and C (3) were only weakly active. The structures of these compounds were determined by spectroscopic methods including MS measurements and NMR analysis.

Animals↗