TMS Derivatives Research Articles

Total Synthesis Analysis of Pseuboyenes D

In this work, we propose a total synthesis route for the antifungal agent Pseuboyenes D, a compound derived from Pseudallescheria boydii CS-793. Pseuboyenes D exhibits antifungal activity comparable to Amphotericin B while offering the advantage of a simpler structure, making it a promising candidate for clinical applications. The system became the focus of this analysis due to its regioselectivity, and after exploration, a [2+2] photocycloaddition and ring expansion strategy was adopted to construct the key bridged ring system. The route employs readily available substrates and mild reaction conditions, making it scalable and suitable for large-scale production. Computational analysis of the regioselectivity of the photocycloaddition revealed that the bridged adduct was thermodynamically favored over the fused system. The synthetic route was further diversified by incorporating functional group modifications using TMS derivatives, enhancing the potential for pharmacological applications. Overall, this work establishes an efficient and scalable synthetic pathway for Pseuboyenes D, paving the way for future applications in antifungal drug development.

Phytochemical characterisation and toxicity effect of Tithonia diversifolia (Hemls.) A. Gray leaf extract on fall army worm Spodoptera frugiperda (JE Smith) larvae.

To mitigate the losses due to fall armyworm (FAW) infestation in maize, chemical pesticides had been the first choice and widely used as an emergency response. However, it comes with attendant health effect. This necessitates the development of plant based effective and safer pesticides. This research investigate response of fall armyworm larvae when they are exposed to crude and partially purified Tithonia diversifolia leaf extract. Chemical constituent of the extract was identified using NIST08.LIB library spectra provided by the software on a GC-MS system and FTIR analysis was done using KBr pellet technique with a resolution and scanning speed of 4 cm-1 and 2 mm/s. Dose dependent toxicity assay of T.diversifolia extracts on FAW at different growth stages under controlled environment in laboratory, followed by its effect under phytotron were examined against control and azadirachtin from neem. The GC-MS of the butanol eluent revealed 20 compounds out of which the major ones being beta-d-glucopyranoside, methyl (15.225 %) palmitic acid, TMS derivative (10.98 %) and hexadecanoic acid, 2-[(trimethylsily)oxy]-, methyl ester (8.75 %). The FT-IR spectroscopic analysis of the butanol eluent of T.diversifolia leaf extract revealed the presence of alcohols, phenols, aldehydes, ketones, alkanes and primary amines. The butanol eluent and crude extract caused 96 % mortality at neonate and first instar FAW larvae. The toxic and repellant effects revealed by diet bioassay and phytotron experiment respectively suggest that butanol eluent of T.diversifolia leaf extract could be a good and effective target for biopesticide production against FAW.

Sudden Death Associated with Propofol Infusion Syndrome

In forensic practice, PRIS is considered as the comorbid disease. The project was devoted to the study of PRIS signs in 38 cases of sudden death after surgical interventions. Archival forensic material of “medical cases” for the period from 2011 to 2020 was studied. The clinical and laboratory features of PRIS are summarized. It was found that the most common symptoms were lactic acidosis, hyperkalemia, and progressive heart failure. Optimization of standard forensic chemical study was carried out, in which it was established that the hydrolysis stage must be included in the urine sample preparation procedure for the determination of propofol. When conducting forensic chemical study of biological objects for the content of propofol, the analytical technologies used must have the sensitivity for detecting propofol in the blood at the level of 0.01 μg/ml or lower. Solid-phase extraction method on cartridges with mixed hydrophobic-anion exchange properties with sorbent such as Oasis MAX Cartridge 3cc, /60 mg/60μm companies Waters (USA) is 17% more effective than the routine liquid-liquid extraction method of propofol from blood. The preparation of TMS derivatives of propofol, increases the efficiency of chromatographic separation and provides the possibility for the analytical study of extracts from blood over a longer period of time (up to 24 hours).

A Comprehensive Chemical Characterization of Leaves of Five Potential Medicinal Plants in Paschim Medinipur District, W. B., India

The physico-chemical and spectroscopic characterization of five selected medicinal plants viz., Acalypha indica, Senna tora, Euphorbia hirta, Physalis angulata and Ziziphus mauritina are the essence and has been carried out to assess bioactive potential and to establish traditional belief in the light of scientific interpretation. Fresh leaves were collected from Paschim Medinipur district of West Bengal, India, dried and powdered for Proximate analysis, ultimate analysis and compositional analysis, FTIR and GCMS. The study revealed that the highest concentration of Volatile matter (75.452%), Bulk density (0.256 %), Swelling index (1.456 %), Cellulose content (61.727 %), Hemicellulose content (4.372 %) and Tannins (0.635 g/ 100g) was observed to occur in Acalypha indica leaf than other experimental plants. In Physalis angulata the percentage composition of fixed carbon (15.251%) and extractive content (1.974 %) was higher than others. Ash content (12.327 %), hemicellulose content (4.372 %), and lignin content (5.531 %) were observed to be higher in the Senna tora leaf than others. Total carbohydrate concentrations (9.619 gm/100 gm) and nitrogen content (2.050 %) were observed to be higher in Euphorbia hirta than others. Total protein (2.321 gm/100 gm), total fat (0.655 gm/100 gm), oxygen content (34.222 %) and Higher heat value (HHV) (16.546 %) were higher in Ziziphus mauritina than others. The existence of functional groups and the relevance of the presence of a specific bioactive component were determined using FTIR (Fourier Transform Infrared Spectroscopy) of the leaves of five plant samples. According to GCMS (Gas Chromatography Mass Spectroscopy), five different medicinal plants contain significant bioactive chemicals. By using GC-MS analysis, a total of 10 bioactive compounds (Acalypha indica, Senna tora) and 8 bioactive compounds (Ziziphus mauritina, Euphorbia hirta, Physalis Angulata) were found in the peaks of methanolic extracts of five potential medicinal plants. The bioactive compounds like Cyclotrisiloxane, Hexamethyl-, Dodecane, 1-Fluoro-, Myo-Inositol, 4-C-Methyl obtained from Acalypha indica leaf extract, Palmitic Acid, Phthalic Acid, Cyclopentadecanol obtained from Senna tora leaf extract and 4-Tert-Octylphenol, TMS Derivative obtained from Euphorbia hirta leaf extract has no records of individual bioactivity as per Dr. Duke’s ethnobotanical and pharmaceutical database and are considered as novel bioactive compounds. Isolation of these compounds and successive bioactivity studies should be the thrust area for future researchers. Also, the current study confirms that specific plant leaves are a great source of important phytochemicals and can be used to make herbal formulations, practical medications, and complementary medicines.

Evaluation of In Vitro Antimicrobial, Antioxidant, and Anti-Quorum Sensing Activity of Edible Mushroom (Agrocybe aegerita).

In the present study, ethanol extract obtained from the mycelial culture of Agrocybe aegerita was evaluated for its antioxidant activity as well for its potential to inhibit the virulence factor responsible for quorum-sensing activity and antibiofilm activity of pathogenic Pseudomonas aeruginosa PAO1 strain. The extract of mushroom at different concentrations showed percentage inhibition in a dose-dependent manner for DPPH and nitric oxide assays with the lowest as 38.56 ± 0.11% and 38.87 ± 0.04% at 50 µg/mL and the highest as 85.63 ± 0.12% and 82.34 ± 0.12% at 200 µg/mL. FTIR analysis confirmed the presence of functional group -OH, O-H bending bonds, C=C stretching, pyranose ring, and H-C-H stretch, confirming the presence of phenol, carotenoid, and ascorbic acid. HPLC analysis revealed that the concentration of gallic acid present in the extract is 27.94 mg/100 g which is significantly (p < 0.05) more than the concentration of rutin (i.e., 7.35 mg/100 g). GC-MS analysis revealed the presence of 5-methyl-1-heptanol, 2-heptadecenal, phthalic acid, butyl hept-4-yl ester, 2-dodecanol, benzoic acid, TMS derivative. The extract showed significantly (p < 0.05) more inhibition of pyocyanin (61.32%) and pyoverdine (54.02%). At higher concentrations of mushroom extract, there was a significant (p < 0.05) reduction (56.32%) in the swarming motility of the test organism. The extract showed 72.35% inhibition in biofilm formation. Therefore, it has been concluded from the present study that mushroom extract, which is rich in phenolic compounds interferes with the virulence factor responsible for quorum sensing, thereby inhibiting biofilm formation, and can be utilized as therapeutic agents against multi-drug resistant pathogenic microorganisms.

A comparative physico-chemical, phytochemical and spectroscopic analysis of two medicinal plants belongs to Euphorbiaceae family: Acalypha indica L. and Euphorbia hirta L. growing in Paschim Medinipur District, West Bengal, India

Plants belong to Euphorbiaceae family, bearing enormous Medicinal potential due to the presence of various pharmacologically important secondary metabolites. Now a days, with the help of various tools and techniques like FTIR, GCMS researchers are engaged to systematically find out various biologically active phytoconstituents. The present study investigated Acalypha indica L. and Euphorbia hirta L. leaf to establish the fact. Physico-chemical parameters of the experimental plants have been investigated. The result shows that Acalypha indica possesses maximum values on Swelling index, volatile matter, ash contents, fixed carbon, higher heat value, hydrogen content, oxygen content, carbon content, hemicellulose content, lignin content and extractive values. In contrast, the percentage composition of bulk density, carbon content, and nitrogen content is higher in Euphorbia hirta. In the present investigation, the FTIR analysis reveals that Acalypha indica L. possessed different chemical classes like Sulfoxide, Alkene, Carbon Dioxide, Alkane, Alcohol etc., whereas FTIR analysis reveals the presence Alkene, Secondary Alcohol, Conjugated Alkene, Carbon Dioxide, Alkene, Alcohol in Euphorbia hirta L. The methanolic leaf extracts of two different plants have been screened through GC-MS, revealing many important bioactive phytoconstituents. Acalypha indica L. possesses Cyclotrisiloxane, Hexamethyl-, cis-2,4-dimethylamine, S, S-dioxide, 1- nonadecanamine, n, n-dimethyl-, tridecane, 2,2,4,10,12,12-hexamethyl-7-(3,5,5-trimethylsilyl)-, dodecane, 1-fluoro-, whereas, Euphorbia hirta L. possesses myo- inositol, 4-c-methyl-, z,z-6,28-heptatriactontadien-2-one, phytylpalmitate, hexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecamethyl-, 4-tert-octylphenol, TMS derivative. Both these plants have chemical substances that have proven bioactivity in human welfare. The GC-MS of leaf methanolic extract reveals that the phytochemical cis-2,4-dimethylthiane, S, S-dioxide have Anticancer (stomach) activities, 1-nonadecanamine, N, N-dimethyl bears Antitumor (nasopharynx) activities, myo-inositol, 4-C- methyl bearing Myo-neuro-stimulant activities and Z, Z-6,28-heptatriactontadien-2-one having Increase zinc bioavailability activities. These activities of individual phytoconstituents have been proven through Dr. Duke's Phytochemical and Ethno-botanical Databases: U.S. Department of Agriculture. This information might be helpful to the pharmacologists, chemists, etc., for future novel drug discovery.

Enzymatic degradation and metabolic pathway of phenanthrene by manglicolous filamentous fungus Trichoderma sp. CNSC-2

Manglicolous filamentous fungi release extracellular lignolytic enzymes that can readily degrade polycyclic aromatic hydrocarbons (PAHs). The present study emphasizes the role of the extracellular enzyme in phenanthrene degradation by the manglicolous fungus Trichoderma sp. CNSC-2 isolated from the Indian Sundarban mangrove ecosystem. The removal efficiency reached 64.05 ± 0.75 % in 50 mg l−1 phenanthrene-amended mineral salt medium at pH 5.6 after 10 days of incubation. Phenanthrene removal was optimized at different pH, nutrient sources, and Cu2+ concentrations. The degradation significantly increased to 67.75 ± 4.32 % at pH 6 (P < 0.0001). The addition of Cu2+ (30 mg l−1) increased the degradation to 78.15 ± 0.36 % (P < 0.0001). The validation experiment confirmed the increase in phenanthrene degradation up to 79.9 ± 1.67 % under optimized conditions. The Lac1 and CytP450 genes encoding for extracellular and intracellular enzymes, respectively, were identified. The GC-MS derived phenanthrene degradation metabolites, i.e., phthalic acid, isobutyl 2-pentyl ester derivative, 1, 2 benzene dicarboxylic acid, butyl 2-methyl propyl ester derivative, TMS derivative of benzoic acid and 3,5 dihydroxy benzoic acid determined two possible metabolic pathways. The laccase enzyme activity was higher in the presence of Phe+Cu2+ (P < 0.0001), indicating the enzyme induction potential of PAH and Cu2+ ions. Purified laccase had a molecular weight of 45 kDa and was highly stable at pH 4–6 and temperature 20–50 °C. The enzyme retained 47 %, 87 %, and 63 % of enzyme activity at 30 mg l−1 concentration of Pb2+, Cd2+, and Hg2+. However, laccase activity was induced by 1.37 folds in the presence of 30 mg l−1 Cu2+ concentration. Thus, the study suggests the potential role of Trichoderma sp. CNSC-2 in phenanthrene degradation.

Phytochemical analysis and nephroprotective potential of Ajwa date in doxorubicin-induced nephrotoxicity rats: Biochemical and molecular docking approaches.

The purpose of this study is to evaluate the likely defensive impact of Ajwa date aqueous extract (AJDAE) in alleviating the nephrotoxicity generated by doxorubicin (DOX) injection in rats. Sixty male Wister albino rats were randomly and equally separated into six groups (n= 10), and they were treated as follows: untreated control group, extract groups administered with 0.75 and 1.5mg kg bw of AJDAE, toxicant control group administered with DOX, and prophylactic groups were treated with 0.75 and 1.5 mg/kg of AJDAE and 15 mg/kg DOX. Biochemical parameters, antioxidant enzymes, renal functions, DNA integrity, and histopathology were studied to evaluate the nephroprotective activity of AJDAE. Furthermore, bioactive compounds were utilized for in silico molecular docking. AJDAE treatment resulted in significant improvements in the amended renal biomarkers (urea, creatinine, calcium, phosphorous, and uric acid), antioxidative markers, and MDA. Noticeable histopathological improvements supported this result. Results of in silico studies revealed that d-Mannitol, 6TMS derivative, palmitic acid, and TMS derivative had a higher docking score with human soluble epoxide hydrolase (-10.9kcal/mol) and NF-κB-DNA (-7kcal/mol). The present findings indicated that AJDAE could decrease ROS generation and lipid peroxidation (LPO) and repair the DOX injection-related DNA damage.

Simple, fast method for the sample preparation of major capsaicinoids in ground peppers, in potato chips and chilli sauces and their analysis by GC-MS

The present work shows the possibility of using the GC-MS method for the qualitative and quantitative determination of major capsaicinoids in ground chillies, chilli sauces and in potato chips with chilli flavoring, which is competitive with already published LC methods. Treatment of samples before GC-MS analysis takes only 30 min. The new method does not require the use of large amounts of organic solvents for extraction or any purification step, as the treatment consists only direct derivatization of major capsaicinoids with hexamethyldisilazane. The new method was validated with a linear calibration range of 0.025–810 µg mL−1 for capsaicin-trimethylsilyl (TMS) and 0.04–440 µg mL−1 for dihydrocapsaicin-TMS. The derivatization efficiency, i.e. the conversion of capsaicin and dihydrocapsaicin to TMS derivatives is 100 % after 30 min of reaction. With the newly developed method, we achieved a good recovery of capsaicin and dihydrocapsaicin in selected ground chilli peppers, chili sauces and potato chips. In the 25 analyzed samples, the capsaicin content was in the range 0.00014–9.86 % and the dihydrocapsaicin content 0.00022–3.45 %, respectively. The suitability of the developed method was confirmed by the agreement of achieved data with that obtained using standard AOAC method in the range less than 5 %. Additionally, this method allows the analysis of samples with a high content of lipid components, sugars, salt or water, which do not interfere with the analysis.

The smell of sex: cuticular hydrocarbons of adult small hive beetles, Aethina tumida (Coleoptera: Nitidulidae)

Cuticular hydrocarbons (CHCs) play key olfactory roles in insect mating, and can therefore be used for pest control. However, the CHC profiles of adult small hive beetles (SHB), Aethina tumida, are currently unknown, even though this widespread invasive species threatens agriculture and wild bee populations. Here we show that CHC profiles can differ between SHB males and females, as well as their mating statuses. In the laboratory, SHB were reared individually and then kept singly or in mixed groups of males and females until sexual maturity at day 10. Then, CHC profiles were compared between the six groups (virgin 1 and 10 days old females, mated 10 days old females, virgin 1 and 10 days old males, and mated 10 days old males). The data show largely homogenous CHC profiles, with no substance being specific to males. However, Hexahydropyridine,1-methyl-4-[4,5-dihydroxyphenyl] was only detected in female SHBs and 2′-Hydroxypropiophenone, TMS derivative was only detected in 10 days old virgin females, and 5-Cyclohexyl-1-pentene was exclusively found in mated beetles, regardless of sex or age. The biological activity of these candidates needs to be confirmed. Given that they constitute olfactory cues involved in mating, this would offer a promising avenue for sustainable pest control of SHB, enabling for the first time to protect wild bee populations.

Phytoconstitutes investigation of Chenopodium ambrosioides Linn. and gas chromatography with mass spectroscopy material analysis

Phytochemical analysis indicated the presence of several biological active secondary compounds like a alkaloids, saponins, phenolics, cardiac glycosides, glycosides, tannins, sterols and flavonoids. Anthraquinones was not detected in leaves and stems of the plant. This study uncovered the plant's total (alkaloids, flavonoids, saponins, tannins, phenolic) percentage. Chenopodium ambrosioides L. was examined for its non-polar components. Crude hexane and chloroform extracts were analyzed using GC–MS, as well as various chromatographic separation mechanisms, were used to identify and characterize (using MASS) seven known ingredients. These substances are, 2-Methoxy-6-Vinylphenol 1, Nandrolone, TMS derivative 2, 2H-1-Benzopyran-2-one, 7-methoxy 3, (E)-Tonghaosu 4, Bisabolol oxide 5, Phytol, TMS derivative 6, (5á)3-Acetoxypregnan-20-ol-6-one-1 8-oic acid lactone 7.

Phytochemical Screening and Assessment of Antioxidant and Antimicrobial Potentialities of Two Egyptian Medicinal Plants

Methanolic extracts of Aerva javanica and Ochradenus baccatus shoots were assessed for their phytoconstituents, antioxidant and antimicrobial activities. Both tested plants displayed potent antioxidant activities evaluated by the DPPH (2, 2-diphenyl-1-picrylhydrazyl), total antioxidant capacity (TAC) and reducing power (EC50) which strongly correlate with their phenolic and flavonoid contents. The antimicrobial study revealed that the methanolic extract of the tested plants exhibited different extents of activities against selected bacterial and fungal strains; moreover, A. javanica was most effective against Pseudomonas aeruginosa. GC-MS analysis of methanolic extracts showed the presence of many compounds in the areal parts of A. javanica like L-Rhamnose; 4TMS derivative, Glycolic acid; TMS derivative, 3-Decen-1-ol, (E)- and 2-Hydroxyisocaproic acid used as antimicrobial agents. On the other hand, for O. baccatus compounds like phosphorodifluoridous hydrazide, trimethyl, palmitic acid and 2-Hydroxyisocaproic acid; TMS derivative which have biological properties as anti-inflammatory and antimicrobial agents were detected. Hence, methanolic extract of A. javanica and O. baccatus shoots have comparatively rich phytochemicals and antioxidants suggesting their desirable use to cure some diseases and disorders. Nevertheless, further isolation and biological screening will elucidate the mechanism of therapeutic potential of these compounds.

Gas Chromatography-Mass Spectrometry Paired with Total Vaporization Solid-Phase Microextraction as a Forensic Tool.

Gas Chromatography - Mass Spectrometry (GC-MS) is a frequently used technique for the analysis of numerous analytes of forensic interest, including controlled substances, ignitable liquids, and explosives. GC-MS can be coupled with Solid-Phase Microextraction (SPME), in which a fiber with a sorptive coating is placed into the headspace above a sample or immersed in a liquid sample. Analytes are sorbed onto the fiber which is then placed inside the heated GC inlet for desorption. Total Vaporization Solid-Phase Microextraction (TV-SPME) utilizes the same technique as immersion SPME but immerses the fiber into a completely vaporized sample extract. This complete vaporization results in a partition between only the vapor phase and the SPME fiber without interference from a liquid phase or any insoluble materials. Depending upon the boiling point of the solvent used, TV-SPME allows for large sample volumes (e.g., up to hundreds of microliters). On-fiber derivatization may also be performed using TV-SPME. TV-SPME has been used to analyze drugs and their metabolites in hair, urine, and saliva. This simple technique has also been applied to street drugs, lipids, fuel samples, post-blast explosive residues, and pollutants in water. This paper highlights the use of TV-SPME to identify illegal adulterants in very small samples (microliter quantities) of alcoholic beverages. Both gamma-hydroxybutyrate (GHB) and gamma-butyrolactone (GBL) were identified at levels that would be found in spiked drinks. Derivatization by a trimethylsilyl agent allowed for conversion of the aqueous matrix and GHB into their TMS derivatives. Overall, TV-SPME is quick, easy, and requires no sample preparation aside from placing the sample into a headspace vial.

Amino Acid Profiles and Bioactive Compounds of Four Inedible Mushrooms from Oban Division of Cross River National Park (CRNP), Nigeria

Inedible mushrooms are endowed with diverse nutritional and nutraceutical compounds. In this study, the amino acid profile, and phytochemical fingerprints of four selected wild inedible mushroom species from Oban Division of Cross River National Park (CRNP), Nigeria including Crepidotus applanatus (Pers.) P. Kumm, Daldinia concentrica (Bolton) Cesati &amp; de Notaris, Oxyporus populinus (Schumach.) Donk and Trametes versicolor (L.) Lloyd were investigated. The fresh sporocarps of study mushroom were collected from the decaying wood during July 2018. Samples for amino acids profiling were dried to constant weight, defatted, hydrolyzed, evaporated in a rotary evaporator and loaded into the cartridge of the Applied Biosystems PTH Amino Acid Analyzer and analyzed for 45 minutes. The samples for phytochemical analysis were subjected to methanol extraction using a Soxhlet extractor and rotatory evaporator and injected into the column of an Agilent gas chromatography mass spectrometer (GCMS). The results of amino acid analysis revealed the presence of ten essential and eight non-essential amino acids in varying quantities across the species. The total amino acid content was highest in C. applanatus followed by D. concentrica, T. versicolor, and O. populinus in decreasing order. Glutamic acid, Arginine, and Aspartic acid were present in the highest amounts while Cystine, Lysine, and Histidine were the least across the species. The phytochemical screening of the samples led to the identification of 24 different compounds in D. concentrica, six compounds each in C. applanatus and O. populinus and three compounds in T. versicolor. In terms of percentage composition, 4H-Imidazo(1,5-a)(1,4)benzodiazepine-3-carboxylic acid, 5,6-dihydro-5-methyl-6-oxo-, ethyl ester, 1-Methylbicyclo[3.2.1]octane, Acetamide, N-(6-acetylaminobenzothiazol-2-yl)-2-(adamantan-1-yl)- and 9,19-Cyclolanost-24-en-3-ol, (3.beta.)-,TMS derivative were the most dominant compounds in C. applanatus, D. concentrica and T. versicolor respectively. The identified compound reportedly shows diverse bioactive activities, including antiviral, anticancer, antioxidant, hypocholesterolemic, anaphylactic, neurostimulant, pesticidal, insecticide and insecticidal activities. This data may represent the baseline information on the amino acid profiles and bioactive constituents of inedible mushroom species from Nigeria, as sources of noble compounds of substantial nutritional, medicinal and agricultural importance.

Inhibitory potential of ethyl acetate extract from mushrooms against root-knot nematode (Meloidogyne incognita)

The present study focused on the nematicidal activities of bio-molecules extracted from mushrooms against M. incognita. The experimental results revealed that the highest hatching inhibition and the juvenile mortality were recorded with the ethyl acetate fraction of cell-free culture (CFC) filtrate of Ganoderma lucidum followed by Lentinus edodes. At 1000 ppm concentration, the bio-active molecules of G. lucidum exhibited the maximum inhibition of egg hatching (92.6%) and juvenile mortality (93.2%) of M. incognita at 72 hours of incubation. GC –MS analysis of G. lucidum revealed the presence of 23 compounds viz. ., Octadecane,3-ethyl-5-(2-ethyl butyl), Decane, Undecane, 3,7-dimethyl-, Dihydroartemisinin, Benzaldehyde, 3,4-dimethyl-, Heptadecane, 2,6,10,15-tetramethyl-, 2,4-Di-tert-butyl-phenol, 1-Propanamine, Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-,1,2-Benzenedicarboxylic acid, butyl octyl ester, n-Hexadecanoic acid, Dibutyl phthalate, 2,2,4-Trimethyl-3-(3,8,12,16-tetramethylheptadeca-3,7,11,15-tetraenyl)-cyclohexanol, Methyl stearate, Cyclohexane, Octadecanoic acid, Deoxyspergualin, Methyl glycocholate, 3TMS derivative, 1,25-dihydroxyvitamin D3, TMS derivative, Spirost-8-en-11-one, 3-hydroxy-, 1H-Indene, 1-hexadecyl-2,3-dihydro- and Bis(2-Ethylhexyl) phthalate. Among these, 2, 4-Di-tert-butyl-phenol, n-Hexadecanoic acid and Dibutyl phthalate might have been responsible for antinemic activity.

Contemporary analytical techniques reveal the secret composition of a 19th century Jerusalem Balsam.

In 1719, Antonio Menzani di Cuna from the Saint Savior monastery published an alcoholic extract formula made from plant and herb resins under the name Jerusalem Balsam. The Balsam gained high popularity due to its remedial benefits. At the end of the 19 th century, Jerusalem Balsam produced by the hermit Johannes Treutler was found to be particularly popular. We analysed a sample of a valuable find coming from the last decade of the 19 th century, making it probably the oldest surviving Jerusalem Balsam in the world. The purpose of this work was to investigate the composition of the historical sample and to try to determine the origin of its components. This was achieved by comparing the profile of volatile compounds extracted from the balsam using HS-SPME technique with the profile characteristic for plant resins as classic ingredients of the Johannes Treutler formula. The use of two chromatographic columns of different polarity, as well as the transformation of the polar components of the sample into TMS derivatives, allowed to obtain new information on the historical composition of the Balsam. Also, it can be stated with high probability that plant resins were indeed used in the production of the Balsam as referred to in the original recipe of Johannes Treutler. We also discuss challenges in determining the original composition of the Balsam.

In‐depth gas chromatography/tandem mass spectrometry fragmentation analysis of formestane and evaluation of mass spectral discrimination of isomeric 3‐keto‐4‐ene hydroxy steroids

The aromatase inhibitor formestane (4-hydroxyandrost-4-ene-3,17-dione) is included in the World Anti-Doping Agency's List of Prohibited Substances in Sport. However, it also occurs endogenously as do its 2-, 6- and 11-hydroxy isomers. The aim of this study is to distinguish the different isomers using gas chromatography/electron ionization mass spectrometry (GC/EI-MS) for enhanced confidence in detection and selectivity for determination. Established derivatization protocols to introduce [2 H9 ]TMS were followed to generate perdeuterotrimethylsilylated and mixed deuterated derivatives for nine different hydroxy steroids, all with 3-keto-4-ene structure. Formestane was additionally labelled with H2 18 O to obtain derivatives doubly labelled with [2 H9 ]TMS and 18 O. GC/EI-MS spectra of labelled and unlabelled TMS derivatives were compared. Proposals for the generation of fragment ions were substantiated by high-resolution MS (GC/QTOFMS) and tandem mass spectrometry (MS/MS) experiments. Subclass-specific fragment ions include m/z 319 for the 6-hydroxy and m/z 219 for the 11-hydroxy compounds. Ions at m/z 415, 356, 341, 313, 269 and 267 were indicative for the 2- and 4-hydroxy compounds. For their discrimination the transition m/z 503 → 269 was selective for formestane. In 2-, 4- and 6-hydroxy steroids loss of a TMSO radical takes place as cleavage of a TMS-derived methyl radical and a neutral loss of (CH3 )2 SiO. Further common fragments were also elucidated. With the help of stable isotope labelling, the structures of postulated diagnostic fragment ions for the different steroidal subclasses were elucidated. 18 O-labelling of the other compounds will be addressed in future studies to substantiate the obtained findings. To increase method sensitivity MS3 may be suitable in future bioanalytical applications requiring discrimination of the 2- and 4-hydroxy compounds.

Mass spectrometric analysis of 7-oxygenated androst-5-ene structures. Influence in trimethylsilyl derivative formation.

The purity of the analyte reference materials was verified by liquid chromatography/quadrupole mass spectrometry. The trimethylsilyl derivatives obtained using several mixtures with MSTFA (N-methyl-N-trimethylsilyl trifluoroacetamide) in comparison with solely MSTFA were analyzed by gas chromatography coupled to a time-of-flight detector equipped with a multimode inlet or to a simple quadrupole detector with a split/splitless inlet. The study showed that the formation of arimistane from 7-oxo-DHEA occurs using common derivatization reagents used for the analyses by gas chromatography (GC). In addition, the formation of the enolized TMS derivative of 7-oxo-DHEA was observed in considerable amount when it was reacted with MSTFA. The analysis of 7α-hydroxy-DHEA resulted in the detection of ~1% of arimistane. The formation of unexpected artifacts from derivatization is influenced by the reagent itself, the reaction temperature, the inlet used and its configuration. The derivatization reagent, instrumental conditions (inlet), as well as the chemical structures of the analytes present in the matrix, can influence the results. So, before describing a new feature as a potential "new" metabolite, special caution must be taken since we could actually be dealing with an artifact.

Alternative markers for Methylnortestosterone misuse in human urine.

Methylnortestosterone is a progestin and synthetic androgenic anabolic steroid, prohibited by WADA. Methylnortestosterone misuse is commonly detected by monitoring the parent compound and its main metabolites, 17α-methyl-5α-estrane-3α, 17β-diol (M1) and 17α-methyl-5β-estrane-3α, 17β-diol (M2), in the glucuronide fraction. In the current study, a direct detection of methylnortestosterone sulfo-conjugated metabolites after ethyl acetate extraction and analysis by LC/Q/TOF-MS in negative ionization mode was performed, detecting two main sulfate metabolites (S1, S2). For the characterization of metabolites, samples from the excretion study, were additionally analyzed by GC-MS, after solvolysis and per TMS derivatization. RT and MS data collected, were compared with RT and MS data from metabolites of 17z-methyl-5α/β-estrane-3α/β, 17z-diols structures with prefixed stereochemistry at 3 and 5 positions, synthesized through Grignard reaction from 19-noretiocholanolone, 19-norandrosterone and 19-norepiandrosterone. Confirmed sulfate metabolites were S1, 17α-methyl-5α-estrane-3α, 17β-diol 3α sulfate (detected up to 72 h) and S2, 17α-methyl-5β-estrane-3α, 17β-diol 3α sulfate (detected up to 192 h). Furthermore, applying targeted analysis based on RT and MS data of the synthesized metabolites two additional metabolites M3, 17β-methyl-5β-estrane-3α, 17α-diol and M4, 17β-methyl-5α-estrane-3α, 17α-diol were detected in the glucuronide fraction and one more metabolite (S3) 17β-methyl-5β-estrane-3α, 17α-diol was detected in the sulfate fraction in lower abundance until the end of the excretion study (192 h). Interestingly, S2 could also be detected after the direct analysis of non-hydrolyzed steroid by GC-MS/MS as artifact, following normal ProcIV anabolic steroid procedure and using diethylether as extraction solvent.

Extraction and intensive conversion of lignocellulose from oil palm solid waste into lignin monomer by the combination of hydrothermal pretreatment and biological treatment

Empty fruit bunches from palm oil production contain lignin, which can be a source of valuable aromatic chemicals such as protocatechuic acid. In this study, empty fruit bunches were utilized in the hydrothermal pretreatment at different temperatures (100–200 °C) to produce liquid fractions containing depolymerized lignin such as single aromatic chemicals. The liquid fractions then underwent microbial processing by a mutant, ∆pcaHG Rhodococcus jostii RHA1 for six days to produce protocatechuic acid. Hydrothermal pretreatment temperature influenced the types of single aromatic chemicals produced and the sum of area of the single aromatic chemicals in both ethyl acetate extracts and TMS derivatives. The single aromatic chemicals obtained at 160 °C, 180 °C, and 200 °C act as precursors to accumulate protocatechuic acid by ∆pcaHG Rhodococcus jostii RHA1 on the third day of incubation. The role of single aromatic chemicals that acted as either precursors or inhibitors of protocatechuic acid was discussed.