Chart of the Nordic and Baltic Seas &c.

[N. 1:4000000].

Chart of the Nordic and Baltic Seas &c.

[N. 1:4000000].

Effect of JJYMD-C, a novel synthetic derivative of gallic acid, on proliferation and phenotype maintenance in rabbit articular chondrocytes in vitro

Tissue engineering encapsulated cells such as chondrocytes in the carrier matrix have been widely used to repair cartilage defects. However, chondrocyte phenotype is easily lost when chondrocytes are expanded in vitro by a process defined as “dedifferentiation”. To ensure successful therapy, an effective pro-chondrogenic agent is necessary to overcome the obstacle of limited cell numbers in the restoration process, and dedifferentiation is a prerequisite. Gallic acid (GA) has been used in the treatment of arthritis, but its biocompatibility is inferior to that of other compounds. In this study, we modified GA by incorporating sulfamonomethoxine sodium and synthesized a sulfonamido-based gallate, JJYMD-C, and evaluated its effect on chondrocyte metabolism. Our results showed that JJYMD-C could effectively increase the levels of the collagen II, Sox9, and aggrecan genes, promote chondrocyte growth, and enhance secretion and synthesis of cartilage extracellular matrix. On the other hand, expression of the collagen I gene was effectively down-regulated, demonstrating inhibition of chondrocyte dedifferentiation by JJYMD-C. Hypertrophy, as a characteristic of chondrocyte ossification, was undetectable in the JJYMD-C groups. We used JJYMD-C at doses of 0.125, 0.25, and 0.5 µg/mL, and the strongest response was observed with 0.25 µg/mL. This study provides a basis for further studies on a novel agent in the treatment of articular cartilage defects.

The adherence of Pseudomonas fluorescens to marble, granite, synthetic polymers, and stainless steel

The adherence of Pseudomonas fluorescens cells to nine food-processing contact surfaces was evaluated using the plate-count method. The surfaces include marble, granite, stainless steel, polyvinyl chloride, polyurethane, and silicone-coated cloth, which have been used only in a few studies concerning bacterial adherence. The number of cells adhered to the surfaces increased with contact time reaching 5.0-6.1 log CDM.cm-2 after 10 hours, which can be considered a well established adherence process. The number of adhered cells doubled in 29.5 minutes and 23.5 minutes on stainless steel and thin polyvinyl chloride-coated cloth, respectively. For the other surfaces, this value was 9.8 minutes on average. Marble, granite, thick polyvinyl-coated cloth, double-faced rugous polyurethane, and silicone-coated cloth were not different (p < 0.05) in their ability to adhere cells (CFU/cm²) after 2 and 10 hours. The surfaces that had higher percentage of similarity in the adhesion level and higher log CFU/cm² of adhered cells were double-faced rugous polyurethane, silicone-coated cloth, and granite. The surfaces showed very different microtopography characteristics when viewed using scanning electron microscopy. This experiment showed the importance of using appropriate materials for food contact during processing, which will affect the cleaning and sanitation procedures.

Conversion of hydroxycinnamic acids into volatile phenols in a synthetic medium and in red wine by Dekkera bruxellensis

The conversion of p-coumaric acid, ferulic acid, and caffeic acid into 4-ethylphenol, 4-ethylguaiacol and 4-ethylcatechol was studied in Dekkera bruxellensis ISA 1791 under defined conditions in a synthetic medium and in a red wine. Liquid chromatography (HPLC-DAD) was used to quantify the phenolic acids, and gas chromatography (GC) coupled to a FID detector was used to quantify volatile phenols using a novel analytical methodology that does not require sample derivatization. Identification was achieved by gas chromatography-mass detection (GC-MS). The results show that phenolic acids concentration decreases while volatile phenols concentration increases. The proportion of caffeic acid taken up by Dekkera bruxellensis is lower than that for p-coumaric or ferulic acid; therefore less 4-ethylcatechol is formed. More important, 4-ethylcathecol synthesis by Dekkera bruxellensis in wine has never been demonstrated so far. These results contribute decisively to a better understanding of the origin of the volatile phenols in wines. The accumulation of these compounds in wine is nowadays regarded as one of the key factors of quality control.

Cytotoxic and genotoxic potential of liquid synthetic food flavorings evaluated alone and in combination

This study aimed to evaluate the cytotoxic and genotoxic potential of food flavorings (Strawberry, Condensed Milk and Chocolate) on Allium cepa meristematic root cells, with exposure times of 24 and 48 hours. Cytotoxic and mutagenic potential were evaluated separately at doses of 0.2, 0.4 and 0.6 ml and in combination, in which for each dose, the same dose of one other flavoring was combined. The results were analyzed by the Chi-square test (p <0.05). The Strawberry flavor in both exposure times and the three studied doses, the Condensed Milk at 0.6 ml in the 48 hour exposure time, the Chocolate flavor at 0.4 ml, exposure time of 48 hours, and at 0.6 ml, in both exposure times and all treatments with combined doses, significantly reduced the cell division rate, proving to be cytotoxic. No treatment resulted in a significant number of cellular aberrations in A. cepa cells, therefore, the flavorings, under the conditions studied, were non- mutagenic.

A map or chart of the Gulfs of Finland and Livonia with their respective ports and harbours, together with a large Plan of Kroonstad and St. Petersburg, taken from an original drawing lately sent from St. Petersburg

Sold by M. Senex at the Globe over against St. Dunstans Church in Fleetstreet London.

Synthetic approaches to syn-diol containing biologically active compounds /

The deoxy derivative of pancratistatin 1.10 was prepared in good yield through the use of a [4+2] Diels-Alder cycloaddition and Bischler-Napieralski cyclization approach. The Bischler-Napieralski cyclization was shown to yield two additional side products 2.9, 2.10, however, under slightly modified hydrolysis conditions, the tetracyclic product 2.11 was obtained exclusively in greater than 84% yield. Initial screening of the di-hydroxylatgd derivative, and the other complementary pair analogue 1.10' previously prepared in our laboratories gave interesting results. Both of these compounds were shown to exhibit cytostatic activity; the mono-alcohol was marginally active while the di-hydroxylated analogue proved to be more potent although one to two magnitudes less potent than pancratistatin itself Human tumour cell line assay results indicated that the di-hydroxylated derivative exhibited selective cytotoxic inhibition in the following cell lines: non-small cell lung cancer line NCI-H226 (ED50 - 0.65 ^g/mL), leukemia cell lines CCRF-CEM (ED30 = 0.55 Hg/mL) and HL-60(TB) (ED50 = 0.89^ig/mL). Our results demonstrated that the pharmacophore is not a mono-alcohol, and that the minimum pharmacophore contains the hydroxyl group at the C4 position in addition to either, or both, of the hydroxyl groups present at C2 and C3.' The minimum pharmacophore has been narrowed to only three possibilities which are current synthetic targets in several research groups. The controlled Grignard addition to the tartaric acid derived bis-Weinreb amide 1.25 afforded a direct entry to a host of 1,4-diflferentiated tartaric acid derived intermediates (2.12-2.18). This potentially usefiil methodology was demonstrated through the efficient synthesis of the naturally occurring lactone 2.23, which bears the inherent syn-dio\ subunit. Based on this result, a similar approach to the synthesis of syn-dio\ bearing natural products looks very promising? A direct 2,3-diol desymmetrization method using TIPS-triflate was shown to be effective on the selective differentiation of Z,-methyl tartrate (and diisopropyl tartrate). The mono-silyl-protected intermediates 2.31 also proved to be useful when they were selectively differentiated at the 1,4-carboxyl position (2.35, 2.36) through the use of a borohydride reducing agent. Furthermore, the mono-silyl-protected derivative underwent periodate cleavage affording two synthetically useful a,P-unsaturated esters 2.43, 2.44, with one of esters being obtained via a silyl-migration method.''

Analyses, persistence an degradation of the synthetic pyrethroid insecticides permethrin and fenvalerate

Studies on persistence and degradation of the synthetic pyrethroid insecticides, permethrin and fenvalerate, were carried out under natural environmental conditions of the Niagara Peninsula. Permethrin and fenvalerate were treated on apple foliage atrat~s of 0.21 kg(AI)!ha and 0.14 kg(AI)/ha, respectively. The initial cis- and trans-permethrin spray deposits were found to be 13.5 ppm and 19.2 ppm, respectively and 38.0 ppm was observed for the fenvalerate treated sample. Twenty-three days and 84 days after spray application, permethrin residues were 4.0 ppm and 2.7 ppm for the cis-isomer, whereas they were 7.9 ppm and 4.7 ppm for the trans-isomer, respectively. Residues of fenvalerate 23 days and 84 days after spray application were 13.4 ppm and 8.0 ppm, respectively. The values of observed half-life of cis-permethrin, trans-permethrin and fenvalerate were found to be 42 days, 46 days and 51 days, respectively. Studies were extended to quantitatively determine some of the major degradation compounds of permethrin and fenvalerate, which were expected to be produced as results of ester cleavage of the parent compounds. A permethrin treated sample, 84 days after initial spray application, showed 0.25 and 0.8 ppm of cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (C12CA (18), respectively. These two acids were not found as free acids, but found as conjugated compounds. The other expected degradation compounds, 3-phenoxybenzyl alcohol (PBalc (~)),3-phenoxybenz.aldehyde (PBald (38)) and 2- (4-chlorophenyl) isovaleric acid (CPIA (31)) were not detected by the methods employed in this study. The results indicate that these degradation compounds were not present, or, if they were present, their concentrations were too low to detect by the methods used.

Synthetic studies on prostaglandins: "synthesis of a new thia-PGEI analog"

A PGE1 analog, namely (±)-trans-2-(6'-carbomethoxyhexyl)-3- (E-3"-thia-1 "-octene)-4-hydroxycyclopentanone 71, has been prepared for the first time. Towards the synthesis of this compound, several synthetic approaches aimed at the preparation of the required acetylenic and E-halovinylic sulfides as building blocks were investigated. Among all the methods examined, it appeared evident that the best route to ethynyl n.pentyl sulfide 81 is via a double dehydrohalogenation of the corresponding 1,2-dibromoethyl sulfide with sodium amide in liquid ammonia. In addition, the isomerically pure E-2-iodoethenyl n.pentyl sulfide 85 is conveniently prepared in high yield and stereoselectivity by hydrozirconation-iodination of the terminal ethynyl sulfide 81. The classical hydroalumination and hydroboration reactions for the preparation of vinyl halides from alkynes gave only small yields when applied as methods towards the synthesis of 85 . The building block 2-(6'-carbomethoxyhexyl)-4-hydroxy-2- cyclopentenone (±)-1 carrying the upper side-chain of prostaglandin E 1 was prepared by a step-wise synthesis involving transformations of compounds possessing the required carbocyclic framework (see scheme 27). The synthesis proved to be convenient and gave a good overall yield of (±)-1 which was protected as the TH P-derivative 37 or the siloxy derivative 38. With the required building blocks 81 and 37 in hand, the target 1S-thia-PGE1 analog (±)-71 was prepared via the in situ higher cuprate formation-conjugate addition reaction. This method proved to be convenient and stereospecific. The standard cuprate method, involving an organocuprate reagent generated from an isolated vinyl iodide, did not work well in our case and gave a complicated mixture of products. The target compound will be submitted for assessment of bio log ical activity.

The suppression of the Haller-Bauer scission for synthetic purposes /|nby S. M. Vines. -- 260 St. Catharines, Ont. : [s. n.],

A number of 2-chlorobenzophenones, containing electron releasing groups (e.g. hydroxy, thiomethoxy and methoxy) in the 4' - position, were prepared by the Friess rearrangement, or the Friedel-Crafts reaction. These ketones, when treated with potassamide in liquid ammonia, underwent partial Haller-Bauer scission, unlike 2-chlorobenzophenone which is known to undergo complete scission. Under similar conditions 4-nitrobenzophenone also underwent partial scission, but the main reaction in this case was nucleophilic amination of the nitro containing ring. This amination reaction was shown not to be a useful general reaction for aromatic nitro compounds. 3-Methylxanthone was then prepared by treatment of 2- and 3- chloro-2'-hydroxy-5'-methylbenzophenone with . little, if any, attendant scission. The corresponding 2fluoro- compound also gave the xanthone, but as the 3-fluoro compound did not, it was concluded that the 2-fluoro compound reacted through a nucleophilic substitution mechanism, rather than the benzyne mechanism invoked for the chloro and bromo compounds. 3-Methylthioxanthone was synthesised by treatment of methyl 4-tolyl sulphide and 2-chlorobenzoyl chloride with aluminum chloride in carbon disu1phide, followed.by heating. This compound was also prepared by treatment of 3-chloro-2'thiomethoxy- 5'-methylbenzophenone with potassamide in liquid ammonia.

Iridium(I) complexes of phenanthroline-derived benzimidazolylidenes : synthetic, structural and catalytic studies

N-heterocyclic carbenes (NHCs) have undergone rapid development in recent years. Due to their strong a-electron donation and structural variability properties, NHCs are becoming a major class of ligands in organometallic chemistry. Compared with the other two types of NHCs (imidazolylidenes and imidazolinylidenes), benzimidazolylidenes have not been well represented. Limited synthetic approaches may impede the development ofbenzimidazolylidenes. This thesis is focused on the synthesis of phenanthroline-derived benzimidazolylidene ligands and their metal complexes. A series of benzimidazolylidene-iridium complexes were synthesized and characterized spectroscopically and crystallographic ally. All of the new complexes showed varying degrees of catalytic activity and enantioselectivity toward transfer hydrogenation and asymmetric hydrogenation. The best results were achieved in hydrogenation of methyl-2-acetamidoacrylate, which afforded (-)-(R)-methyl-2-acetamidopropanoate in 97% yield and 81 % ee.

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month ending Dec. 1, 1854

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month ending Dec. 1, 1854, signed by S.D. Woodruff, Jan. 1855.

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the month of Jan. 1855, signed by S.D. Woodruff, Feb. 1855.

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell

Chart of estimate of work done on the Port Dalhousie and Thorold Railway by Messrs. Brown and McDonell, contractors, on sections 1, 2, and 3 ending at St. Catharines for the months of Feb. and March, 1855, signed by S.D. Woodruff, Apr. 1855.