Novel Secondary Metabolites from New Zealand Marine Sponges

<p>The isolation and structure elucidation of 12 new compounds from four different genera of marine sponge is described. Continued work with the marine sponge Raspailia topsenti resulted in the isolation of two clerodane diterpenes, raspailodanes F (40) and G (41). Raspailodane F contains a novel tricyclo[5.4.0.0]undecane scaffold including a cyclopropyl ring. A nonadecanoic acid derivative, petrosianoic acid (122), was isolated from an unknown species of the genus Petrosia. It is believed that 122 is only the third nonadecanoic acid derivative reported from the marine environment. The marine sponge Dendrilla rosea was examined for the presence of new spongian diterpenes. While no new diterpenes were discovered, the acetylenic nitrile dendronitrile (158) was isolated along with two known diterpenes and a known steroid. Dendronitrile is the first acetylenic nitrile discovered from the marine environment and only the third ever reported. Seven new lamellarins and one new dictyodendrin were isolated from Dictyodendrilla dendyi alongside one known lamellarin and two known dictyodendrins. Lamellarins Θ (187) and κ (188) are related to known lamellarins. The remaining five lamellarins are sulfated derivatives, lamellarin Θ 4'',4'''-disulfate (190), lamellarin O 4'''-sulfate (191), lamellarin O 4'',4'''-disulfate (192), lamellarin κ 4'''-sulfate (193), and lamellarin κ 4'',4'''- disulfate (194). Dictyodendrin F (195) is a new natural product previously only reported as a semi-synthetic derivative of known dictyodendrins. Lamellarin shows moderate cytotoxic activity. The biological activity of the remaining compounds, particularly the sulfated derivatives, is under investigation. The screening protocol used to analyse crude sponge extracts was refined and a number of advances were made towards the automated analysis of the spectra generated. A method was devised to extract peak data from screen HSQC spectra and by combining these data, to produce a software-based mask of known correlations. The application of this mask was demonstrated in three different ways to three different screen HSQC spectra. To aid in the identification of interesting correlations identified by the mask, a database of HSQC correlations was compiled from literature and in-house sources. A new method of describing the chemical environment of a given position was developed to suit the needs of the database. At present, the database contains 91 compounds and represents over 2500 individual HSQC correlations. Development of both the software screening technique and the HSQC correlation database is ongoing.</p>

Novel Secondary Metabolites from New Zealand Marine Sponges

<p>The isolation and structure elucidation of 12 new compounds from four different genera of marine sponge is described. Continued work with the marine sponge Raspailia topsenti resulted in the isolation of two clerodane diterpenes, raspailodanes F (40) and G (41). Raspailodane F contains a novel tricyclo[5.4.0.0]undecane scaffold including a cyclopropyl ring. A nonadecanoic acid derivative, petrosianoic acid (122), was isolated from an unknown species of the genus Petrosia. It is believed that 122 is only the third nonadecanoic acid derivative reported from the marine environment. The marine sponge Dendrilla rosea was examined for the presence of new spongian diterpenes. While no new diterpenes were discovered, the acetylenic nitrile dendronitrile (158) was isolated along with two known diterpenes and a known steroid. Dendronitrile is the first acetylenic nitrile discovered from the marine environment and only the third ever reported. Seven new lamellarins and one new dictyodendrin were isolated from Dictyodendrilla dendyi alongside one known lamellarin and two known dictyodendrins. Lamellarins Θ (187) and κ (188) are related to known lamellarins. The remaining five lamellarins are sulfated derivatives, lamellarin Θ 4'',4'''-disulfate (190), lamellarin O 4'''-sulfate (191), lamellarin O 4'',4'''-disulfate (192), lamellarin κ 4'''-sulfate (193), and lamellarin κ 4'',4'''- disulfate (194). Dictyodendrin F (195) is a new natural product previously only reported as a semi-synthetic derivative of known dictyodendrins. Lamellarin shows moderate cytotoxic activity. The biological activity of the remaining compounds, particularly the sulfated derivatives, is under investigation. The screening protocol used to analyse crude sponge extracts was refined and a number of advances were made towards the automated analysis of the spectra generated. A method was devised to extract peak data from screen HSQC spectra and by combining these data, to produce a software-based mask of known correlations. The application of this mask was demonstrated in three different ways to three different screen HSQC spectra. To aid in the identification of interesting correlations identified by the mask, a database of HSQC correlations was compiled from literature and in-house sources. A new method of describing the chemical environment of a given position was developed to suit the needs of the database. At present, the database contains 91 compounds and represents over 2500 individual HSQC correlations. Development of both the software screening technique and the HSQC correlation database is ongoing.</p>

Metabolomics Profiling Discriminates Prostate Cancer From Benign Prostatic Hyperplasia Within the Prostate-Specific Antigen Gray Zone

ObjectiveProstate cancer (PCa) is the second most common male malignancy globally. Prostate-specific antigen (PSA) is an important biomarker for PCa diagnosis. However, it is not accurate in the diagnostic gray zone of 4–10 ng/ml of PSA. In the current study, the performance of serum metabolomics profiling in discriminating PCa patients from benign prostatic hyperplasia (BPH) individuals with a PSA concentration in the range of 4–10 ng/ml was explored.MethodsA total of 220 individuals, including patients diagnosed with PCa and BPH within PSA levels in the range of 4–10 ng/ml and healthy controls, were enrolled in the study. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS)-based non-targeted metabolomics method was utilized to characterize serum metabolic profiles of participants. Principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) methods were used for multivariate analysis. Receiver operating characteristic (ROC) curve analysis was performed to explore the diagnostic value of candidate metabolites in differentiating PCa from BPH. Correlation analysis was conducted to explore the relationship between serum metabolites and common clinically used fasting lipid profiles.ResultsSeveral differential metabolites were identified. The top enriched pathways in PCa subjects such as glycerophospholipid and glycerolipid metabolisms were associated with lipid metabolism. Lipids and lipid-like compounds were the predominant metabolites within the top 50 differential metabolites selected using fold-change threshold &gt;1.5 or &lt;2/3, variable importance in projection (VIP) &gt; 1, and Student’s t-test threshold p &lt; 0.05. Eighteen lipid or lipid-related metabolites were selected including 4-oxoretinol, anandamide, palmitic acid, glycerol 1-hexadecanoate, dl-dihydrosphingosine, 2-methoxy-6Z-hexadecenoic acid, 3-oxo-nonadecanoic acid, 2-hydroxy-nonadecanoic acid, N-palmitoyl glycine, 2-palmitoylglycerol, hexadecenal, d-erythro-sphingosine C-15, N-methyl arachidonoyl amine, 9-octadecenal, hexadecyl acetyl glycerol, 1-(9Z-pentadecenoyl)-2-eicosanoyl-glycero-3-phosphate, 3Z,6Z,9Z-octadecatriene, and glycidyl stearate. Selected metabolites effectively discriminated PCa from BPH when PSA levels were in the range of 4–10 ng/ml (area under the curve (AUC) &gt; 0.80). Notably, the 18 identified metabolites were negatively corrected with total cholesterol (TC), low-density lipoprotein cholesterol (LDL-C), and Apo-B levels in PCa patients; and some were negatively correlated with high-density lipoprotein cholesterol (HDL-C) and Apo-A levels. However, the metabolites were not correlated with triglycerides (TG).ConclusionThe findings of the present study indicate that metabolic reprogramming, mainly lipid metabolism, is a key signature of PCa. The 18 lipid or lipid-associated metabolites identified in this study are potential diagnostic markers for differential diagnosis of PCa patients and BPH individuals within a PSA level in the gray zone of 4–10 ng/ml.

Biofortification of Hens Eggs with Polyunsaturated Fatty Acids by New Dietary Formulation: Supercritical Microalgal Extract

The aim of the study was to evaluate the effect of Spirulina platensis, formulation containing microalgal extract, post-extraction residue, and formulation without algal extract (containing only emulsifier) on the content of FAs in the eggs of laying hens. The experiment was conducted on 90 laying hens (ISA Brown) as a completely randomized design. Hens were assigned to five experimental groups (six replicates). The FAs content in eggs was determined after 30, 60, 90, and 120 days of the experiment. There were no statistically significant differences in FA profiles after 30 days of the experiment. It was shown that after 60, 90, and 120 days of the experiment, the investigated additives had a significant impact on the content of such acids as: dodecanoic acid (C12:0), C15:0, nonadecanoic acid (C19:0), myristoleic acid (C14:1 n-5), α-linolenic acid (ALA, C18:3 n-3), DPA, C20:2 n-6, and decosahexaenoic acid (DHA C22:6 n-6). There were also significant differences in total PUFA n-3, PUFA n-6, and n-6/n-3 ratio in eggs. The obtained results suggest that the use of algae extract and emulsifier in laying hens nutrition has the greatest impact on the FA profile in the eggs.

Profil Minyak Biji dari Empat Varietas Rosela Herbal (Hisbiscus sabdariffa var. sabdariffa) Indonesia

<p>Rosela herbal dibudidayakan untuk diambil kalik (kelopak bunga) sebagai bahan baku minuman herbal. Produk samping dari budidaya rosela herbal salah satunya adalah biji rosela. Penelitian ini dilakukan untuk mengevaluasi komposisi senyawa asam lemak dan kadar minyak biji rosella dari empat varietas unggul rosella herbal (Roselindo 1, Roselindo 2, Roselindo 3, dan Roselindo 4 dan membahas potensinya sebagai bahan pangan). Minyak biji rosella herbal diekstrak dengan cara pengepresan dan analisa profil asam lemak dengan metode GCMS. Biji rosela herbal mempunyai kadar minyak yang cukup tinggi, yaitu antara 23,25 – 27,31%. Asam linoleat, asam oleat, asam palmitat dan asam nonadekanoat adalah asam lemak utama pada empat varietas rosela herbal. Pengelompokan varietas rosela berdasarkan persentase kemiripan kandungan minyak dan asam lemak menunjukkan bahwa Roselindo 1 berada dalam satu kelompok dengan Roselindo 3 dan Roselindo 2 dengan Roselindo 4. Senyawa asam lemak dari Roselindo 1 dan Roselindo 3 asam adalah dari kelompok asam lemak tak jenuh (UFA) yakni asam linoleat pada Roselindo 1 dan asam oleat pada Roselindo 3. Senyawa asam lemak utama varietas Roselindo 2 dan Roselindo 4 adalah asam nonadekanoat. Berdasarkan jenis asam lemak tersebut maka minyak biji rosella termasuk dalam kategori minyak yang aman dikonsumsi (<em>edible oil</em>) dan juga berkhasiat bagi kesehatan.</p><div><hr align="left" size="1" width="33%" /><div><p align="center"><strong>Profile of Four <strong>Varieties of </strong>Indonesian Herbal Roselle (<em>Hisbiscus sabdariffa</em> var. <em>sabdariffa</em>) </strong></p><p>Herbal roselle is cultivated for calices production as raw material for herbal drinks. One of the by products from herbal roselle cultivation is roselle seeds. This study was conducted to evaluate the composition of fatty acid compounds and roselle seed oil content of four herbal roselle superior varieties (Roselindo 1, Roselindo 2, Roselindo 3, and Roselindo and discuss their potency as a foodstuff 4). Herbal roselle seed oil is extracted using pressing method and analyzing fatty acid profiles using GC-MS method. Herbal roselle seeds have high oil content, i.e., 23.25 - 27.31%. Linoleic acid, oleic acid, palmitic acid and nonadecanoic acid are the main fatty acids in four herbal rosela varieties. The grouping of rosela varieties based on the percentage similarity of oil content and fatty acids shows that Roselindo 1 is in one group with Roselindo 3 and Roselindo 2 with Roselindo 4. The main fatty acids of Roselindo 1 and Roselindo 3 are from a group of unsaturated fatty acids (UFA), namely linoleic acid on Roselindo 1, and oleic acid in Roselindo 3 The main fatty acid compounds of Roselindo 2 and Roselindo 4 are nonadecanoic acid. Based on these types of fatty acids, rosella seed oil of Roselindo varieties is in the category of edible oil and is also beneficial for health.</p></div></div>

Solena amplexicaulis (Cucurbitaceae) flower surface wax influencing attraction of a generalist insect herbivore, Aulacophora foveicollis (Coleoptera: Chrysomelidae)

Aulacophora foveicollisLucas causes economic losses to creeping cucumber [Solena amplexicaulis(Lam.) Gandhi] growers in India and Bangladesh because adults feed on the leaves and flowers causing death of the plant. The insect is a generalist herbivore as it also causes damage to pumpkin, bottle gourd, sponge-gourd and gac fruit production by feeding on leaves and flowers of these plants. At present, insects are controlled with insecticides, which are harmful to human health and the environment. We studied the behavioural responses of adultA. foveicollisto flower surface waxes and synthetic compounds mimicking flower surface waxes to determine their potential for monitoring this pest. The gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detector (GC-FID) analyses ofS. amplexicaulisflower (50 g) surface waxes indicated presence of 17.9 and 3.1 mg alkanes and free fatty acids, respectively. Seventeenn-alkanes fromn-C15ton-C34and 16 free fatty acids from C10:0 to C22:0 were detected in the flower surface waxes. Heptacosane was predominant amongn-alkanes representing 2748.1 µg; whereas, pentadecanoic acid was the major fatty acid accounting for 466.6 µg.Aulacophora foveicolliswere attracted to the flower surface waxes at concentrations of 4 to 8 μg/ml, as demonstrated by a Y-tube olfactometer bioassay. Using a dose response bioassay, the insect was shown to be attracted to individual synthetic pentadecane, heptacosane, nonacosane, undecanoic acid and nonadecanoic acid at 0.70, 0.70, 1.20, 1.60 and 1.40 µg/ml, respectively. The insect displayed highest attraction to a synthetic mixture of 0.70, 1.23, 0.77, 0.84, 0.94 and 0.74 µg/ml of pentadecane, heptacosane, nonacosane, undecanoic acid, lauric acid and nonadecanoic acid, respectively, and hence, this combination might be used for insect pest management such as in baited traps.