Diaporthe phaseolorum, an endophyte isolated from Combretum lanceolatum, has exhibited diverse biological activities including antimicrobial, leishmanicidal, antitumoral, and herbicidal properties. Regardless of these activities, there remains limited research on its chemical constituents. Therefore, this study aimed to investigate the metabolome of D. phaseolorum employing mass spectrometry data dereplication through molecular networking and MolNetEnhancer tools. Twenty two molecular families were annotated, including prenol lipids, benzenoids, organoheterocyclic compounds, and nucleosides. Among the 41 nodes annotated, 36 metabolites were confirmed via spectral references, including alismol, farnesol, linoleic acid, tyramine, N-acetyl-tyramine, 5-methoxy-1H-indole-3-carbaldehyde, 6-pentyl-2H-pyran-2-one, and adenosine. Further node annotation was achieved through MolNetEnhancer, resulting in the classification of an additional 68 nodes into various molecular families. Consequently, this study represents a significant contribution to the identification of the D. phaseolorum metabolome, highlighting its secondary metabolites and providing valuable chemical insights to elucidate its demonstrated biological activities. lanceolatum antimicrobial leishmanicidal antitumoral properties constituents Therefore D tools annotated lipids benzenoids compounds nucleosides 4 3 references alismol farnesol acid tyramine Nacetyltyramine, Nacetyltyramine N acetyl N-acetyl-tyramine 5methoxy1Hindole3carbaldehyde, 5methoxy1Hindole3carbaldehyde methoxyHindolecarbaldehyde 5 methoxy 1H indole carbaldehyde, carbaldehyde H 5-methoxy-1H-indole-3-carbaldehyde 6pentyl2Hpyran2one, 6pentyl2Hpyran2one pentylHpyranone 6 pentyl 2H pyran 2 one, one 6-pentyl-2H-pyran-2-one adenosine Consequently Hindole Hpyran

This study aims to propose a new method for derivatizing fatty acids (FAs) from human milk (HM), eliminating the lipid extraction step, and simplifying the preparation for gas chromatography with a flame ionization detection (GC-FID) analysis to quantify the FAs. The Design Expert software optimized the reaction times, concentrations, and sample amount. The proposed method (PM) was validated for lyophilized HM and results for the figures of merit for precision in relative standard deviation (RSD) (RSDintra-day 1.34-4.03% and RSDinter day 2.08 5.16%), accuracy (99.87-102.16%), and robustness are within a linear range of 3 to 38% lipids in HM samples. The atmospheric solids analysis probe tandem mass spectrometry (ASAP-MS/MS) technique confirmed the efficiency of PM by expressing the molecular composition of triacylglycerol formed by FAs from the GC-FID technique. The PM requires a small sample size and conducts derivatization directly in the sample matrix, minimizing extraction errors. (FAs HM, , (HM) step GCFID GC FID (GC-FID times concentrations amount (PM RSD (RSD RSDintraday RSDintra 1.344.03% 134403 1.34 4.03% 1 34 4 03 1.34-4.03 208 2 08 2.0 5.16%, 516 5.16% 5 16 5.16%) 99.87102.16%, 998710216 99.87 102.16% 99 87 102 (99.87-102.16%) 38 samples ASAPMS/MS ASAPMSMS ASAP MS/MS MS (ASAP-MS/MS matrix errors (HM 344 1.344.03 13440 134 1.3 403 4.03 0 1.34-4.0 20 2. 51 5.16 87102 99.87102.16% 99871021 9987 99.8 10216 102.16 9 8 10 (99.87-102.16% ASAPMS MSMS 1.344.0 1344 13 1. 40 4.0 1.34-4. 5.1 8710 99.87102.16 9987102 998 99. 1021 102.1 (99.87-102.16 1.344. 4. 1.34-4 5. 871 99.87102.1 998710 102. (99.87-102.1 1.344 1.34- 99.87102. 99871 (99.87-102. 99.87102 (99.87-102 99.8710 (99.87-10 99.871 (99.87-1 (99.87- (99.87 (99.8 (99. (99 (9 (

In this work, a miniaturized version of the QuEChERS (quick, easy, cheap, effective, rugged, and safe) method was optimized, validated, and applied for extracting eight pesticide residues in anuran liver tissue samples. The extracts were quantified by high-performance liquid chromatography with diode array detection, and the detected residues in liver tissue samples were identified by tandem mass spectrometry-liquid chromatography. The optimized extraction method entailed the scale reduction of the QuEChERS method twenty times using 500 mg of liver tissue sample, 200 mg Mg2SO4, 50 mg NaCl, 1.5 mL of acetonitrile, and a mixture of 25 mg C18 + 25 mg PSA (primary-secondary amine) as dispersive solid-phase extraction sorbent. The method was validated using liver tissue samples spiked at two levels of pesticide concentrations according to the SANTE/11312/2021 document. Recoveries ranged from 91-110% with a relative standard deviation < 20%. The method robustness assessed by the Steiner and Youden test resulted in recovery rate variations of less than 2% for all pesticides after deliberated changes in seven variables. The validated method was applied to 72 liver tissue samples from two anuran species, registering residues of some pesticides in 31 samples. The proposed method proved to be efficient, precise, and robust for determining pesticide residues in anuran liver tissues. work quick, quick (quick easy cheap effective rugged safe highperformance high performance detection spectrometryliquid spectrometry sample 20 Mg2SO4 MgSO Mg SO 5 NaCl 15 1 1. acetonitrile 2 C C1 primarysecondary primary secondary amine solidphase solid phase sorbent SANTE113122021 SANTE 11312 2021 SANTE/11312/202 document 91110% 91110 91 110% 110 91-110 20% variables 7 species 3 efficient precise tissues Mg2SO SANTE11312202 1131 202 SANTE/11312/20 9111 9 11 91-11 SANTE1131220 113 SANTE/11312/2 911 91-1 SANTE113122 SANTE/11312/ 91- SANTE11312 SANTE/11312 SANTE1131 SANTE/1131 SANTE113 SANTE/113 SANTE11 SANTE/11 SANTE1 SANTE/1 SANTE/

In the Amazon, Euterpe oleracea Mart. (açaí), is part of the identity of traditional communities, and the fruit is integrated into their everyday sociocultural dynamics. Hydrolysis and pyrolysis of residual biomass can be alternatives to yield sugars, ethanol, biochar and bio-oil. The açaí seeds subjected to oxidative pretreatment followed by acid hydrolysis increased cellulose to fermentable sugars (reaching 23.5%) and second-generation ethanol production (17.441 L t−1). Açaí oil (ca. 30%) was extracted using a Soxhlet apparatus (using hexane as solvent) and detected through gas chromatography coupled to mass spectrometry (GC-MS), where acids accounted for 82.43% of the total composition, while alcohols comprised only 13.15%. For pyrolysis, temperatures (500 and 550 °C), time (20 and 30 min), and activation temperature (750 and 800 °C) were evaluated, resulting in yields of ca. 22% for biochar and 30% for bio-oil. For the bio-oil, the main compounds detected by GC-MS were acids (16.3%), aldehydes (13.08%), amides (12.19%), alcohols (6.72%), and phenols (4.64%). The obtained biochar displayed surface area values of 553.7 m2 g−1 and 10% crystallinity, indicating its more amorphous nature. Amazon Mart açaí, , (açaí) communities dynamics biooil. biooil bio oil. bio-oil reaching 23.5% 235 23 5 secondgeneration second generation 17.441 17441 17 441 (17.44 t−1. t1 t t−1 . 1 t−1) ca (ca solvent GCMS, GCMS GC MS (GC-MS) 8243 82 43 82.43 composition 1315 13 15 13.15% 500 (50 55 °C, C °C 20 (2 3 min, min min) 750 (75 80 evaluated 22 biooil, oil, 16.3%, 163 16.3% 16 (16.3%) 13.08%, 1308 13.08% 08 (13.08%) 12.19%, 1219 12.19% 12 19 (12.19%) 6.72%, 672 6.72% 6 72 (6.72%) 4.64%. 464 4.64% 4 64 (4.64%) 5537 553 7 553. m g1 g g− 10 crystallinity nature (açaí 23.5 2 17.44 1744 44 (17.4 t− (GC-MS 824 8 82.4 131 13.15 50 (5 ( 75 (7 16.3 (16.3% 130 13.08 0 (13.08% 121 12.19 (12.19% 67 6.72 (6.72% 46 4.64 (4.64% 23. 17.4 174 (17. 82. 13.1 16. (16.3 13.0 (13.08 12.1 (12.19 6.7 (6.72 4.6 (4.64 17. (17 13. (16. (13.0 12. (12.1 6. (6.7 4. (4.6 (1 (16 (13. (12. (6. (4. (13 (12 (6 (4

Alzheimer’s disease (AD) is a neurodegenerative disorder characterized by extracellular accumulation of amyloid-β (Aβ) peptides in the brain. This study demonstrates the direct association of the disposable pipette extraction (DPX) with tandem mass spectrometry (MS/MS) for the analysis of Aβ peptides in cerebrospinal fluid (CSF) samples. Different parameters were optimized in order to improve detectability in the MS/MS including mobile phase percentage of ammonium hydroxide, mobile phase flow rate and acquisition mode. Also, this method used an electrospray ionization (ESI) low-flow probe and direct infusion of an organic solution in the MS/MS. The DPX-MS/MS method showed adequate linearity for determining Aβ peptides in CSF-linearity ranged from 0.1 to 1.5 ng mL 1. The coefficients of determination were higher than 0.99; the precision coefficient of variation (CV) ranged from 0.3 to 12.7%; and the accuracy relative standard deviation (RSD) ranged from -13.6 to 13.2%. Alzheimers Alzheimer s AD (AD amyloidβ amyloid β (Aβ brain DPX (DPX MSMS MS (MS/MS CSF (CSF samples hydroxide mode Also ESI (ESI lowflow low DPXMS/MS DPXMSMS CSFlinearity 01 0 1 0. 15 5 0.99 099 99 CV (CV 03 3 12.7% 127 12 7 RSD (RSD 13.6 136 13 6 -13. 132 2 13.2% DPXMS 0.9 09 9 12.7 13. -13 13.2 12. -1 -

This study expands and shows the versatility of applications in hydrophilic interaction chromatography coupled with triple quadrupole mass spectrometry (HILIC-MS/MS) using a FRULIC-N column to determine 31 phenolic compounds in beverage industry residues (coffee, apple juice, beer, and wine). Optimization, via Doehlert design, determined the acetonitrile proportion (50-90%) and pH (3.0-7.0) in the mobile phase (MP). A 22 factorial design assessed the concentration of ammonium acetate (10-110 mmol L-1) in the MP and column temperature (20-60 °C). Injection volume (5-45 µL) was univariately optimized. Separations at 60 °C reduced chromatographic run time to less than 11 min. Gradient elution (500 µL min-1) employed an MP comprising acetonitrile and ammonium acetate (110 mmol L-1, pH 7). Validation demonstrated average coefficient of determination (R2) 0.9707, limit of detection 0.001-0.503 mg L-1 and quantification 0.004-1.524 mg L-1, precision < 12.2%, recovery 92.4-110.8%. The method was applied to five residues, indicating its viability for determining phenolics in beverage production residues. HILICMS/MS HILICMSMS HILIC MS/MS MS (HILIC-MS/MS FRULICN FRULIC N 3 coffee, coffee (coffee juice beer wine. wine . wine) Optimization 5090% 5090 50 90% 90 (50-90% 3.07.0 3070 3.0 7.0 0 7 (3.0-7.0 MP. (MP) 2 10110 10 110 (10-11 L1 L 1 2060 20 (20-6 °C. C °C) 545 5 45 (5-4 optimized 6 min 500 (50 min1 min-1 (11 L1, 1, 7. 7) R2 R (R2 09707 9707 0.9707 0.0010.503 00010503 0.001 0.503 001 503 0.001-0.50 L- 0.0041.524 00041524 0.004 1.524 004 524 0.004-1.52 122 12 12.2% 92.4110.8%. 9241108 92.4 110.8%. 92 4 8 92.4-110.8% HILICMS MSMS 509 9 (50-90 07 3.07. 307 30 3. 70 (3.0-7. (MP 1011 (10-1 206 (20- 54 (5- (5 min- (1 (R 0970 970 0.970 0010 0.0010.50 0001050 0001 0.00 0503 0.50 00 0.001-0.5 0041 0.0041.52 0004152 0004 1524 1.52 52 0.004-1.5 12.2 4110 92.4110.8% 924110 924 92. 1108 110.8% 92.4-110.8 (50-9 3.07 (3.0-7 101 (10- (20 ( 097 97 0.97 0.0010.5 000105 000 0.0 050 0.5 0.001-0. 0.0041.5 000415 152 1.5 0.004-1. 12. 411 92.4110.8 92411 110.8 92.4-110. (50- (3.0- (10 (2 09 0.9 0.0010. 00010 0. 05 0.001-0 0.0041. 00041 15 1. 0.004-1 41 92.4110. 9241 110. 92.4-110 (3.0 0.0010 0.001- 0.0041 0.004- 92.4110 92.4-11 (3. 92.411 92.4-1 (3 92.41 92.4-

Acetic acid bacteria (AAB) are versatile organisms that catalyze the conversion of a wide range of carbon sources into biomolecules of great industrial interest. In this study, we exploited the ability of Gluconobacter spp. to synthesize levans. Among the isolated strains, Gluconobacter cerinus UELBM11 produced approximately 14.0 g L−1 of levan under non-optimized conditions. Gas chromatography-mass spectrometry (GC-MS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR) analyses confirmed that levan obtained from G. cerinus UELBM11 consisted of a β-(2→6)-D-fructose backbone with some β-(2→1) ramifications. The average molecular weight (Mw) of the purified levan was 8.78 × 105 Da. Thermogravimetric/differential thermogravimetric (TGA/DTG) analysis indicated high thermal stability, with the maximum decomposition rate observed at 227.44 °C. Scanning electron microscopy (SEM) revealed a microporous morphology, and the antioxidant activity assays demonstrated that levan had a high scavenging capacity of 2,2’-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and hydroxyl radicals. Therefore, it has been demonstrated the levan produced by G. cerinus UELBM11 is a promising natural antioxidant and, owing to its microporosity and excellent thermal properties and stability, is a potential candidate as an additive in cosmetics, pharmaceuticals, and food products. AAB (AAB interest study spp levans strains UELBM UELBM1 140 14 0 14. L1 L 1 L− nonoptimized non optimized conditions chromatographymass chromatography mass GCMS, GCMS GC MS , (GC-MS) FTIR, FTIR (FTIR) NMR (NMR G β2→6Dfructose β26Dfructose βDfructose β 2→6 D fructose 2 6 β2→1 β21 2→1 β-(2→1 ramifications Mw (Mw 878 8 78 8.7 10 Da Thermogravimetricdifferential Thermogravimetric differential TGA/DTG TGADTG TGA DTG (TGA/DTG stability 22744 227 44 227.4 C °C SEM (SEM morphology 2,2azinobis 22azinobis azinobis 2,2 azino bis 3ethylbenzothiazoline6sulfonic ethylbenzothiazolinesulfonic 3 ethylbenzothiazoline sulfonic ABTS (ABTS radicals Therefore cosmetics pharmaceuticals products (GC-MS (FTIR β2 6Dfructose Dfructose 26 2→ β2→ 21 β-(2→ 87 7 8. 2274 22 4 227. 2azinobis 2, β-(2 β-( β-

APPLICATION OF MASS SPECTROMETRY WITH PAPER SPRAY IONIZATION AND THE OPLS-DA CHEMOMETRIC METHOD FOR THE DIAGNOSIS OF PROSTATE CANCER BY ANALYSIS OF URINE SAMPLES. In this study, paper spray ionization mass spectrometry (PSI-MS) allied to orthogonal projections on the latent structure-discrimination analysis (OPLS-DA) was employed to differentiate urine samples from patients with prostate cancer and control individuals (without prostate cancer). The parameters of sensitivity, specificity, efficiency and Matthew’s correlation coefficient determined to analyze the efficiency and quality of the OPLS-DA model obtained a value equal to 1, which means, respectively, that the model has a good performance to correctly classify true positive samples and true negatives. These results showed 100% correct classification of the samples from the training and test set, demonstrating a high efficiency of the OPLS-DA model when classifying all samples considered as belonging to the class of interest (urine from control patient) into class 1 and all samples considered as belonging to the non-interest class (urine from patients with prostate cancer) in class 0. This efficiency resulting from the application of this model suggests that the PSI-MS combined to OPLS-DA is a promisor approach for a rapid diagnosis of prostate cancer, via chemical fingerprints of urine samples. OPLSDA OPLS DA SAMPLES study PSIMS PSI MS (PSI-MS structurediscrimination structure discrimination (OPLS-DA without cancer. . sensitivity specificity Matthews Matthew s means respectively negatives 100 set patient noninterest non 0 10

Bredemeyera Willd. is a genus of the Polygalaceae family, occurring in Brazil. This research aims to evaluate the phytochemical and antifungal potential, in vitro and in silico, of Bredemeyera brevifolia extracts. The identification of fatty acids by gas chromatography-mass spectrometry and their quantification by gas chromatography-flame ionization detector showed that palmitic (36.55 mg g−1), margaric (3.66 mg g−1), linolelaidic (108.82 mg g−1), oleic (7.86 mg g−1), stearic (41.11 mg g−1), dihomo-γ-linolenic (85.48 mg g−1), and arachidic (209.00 mg g−1) acids are present in the hexane extract. From the chloroform extract, 1-hydroxy-3,7-dimethoxyxanthone was isolated and identified. The minimum inhibitory concentration assay with methanolic extract demonstrated antifungal activity against species of the genus Candida, Sporothrix, and Trichophyton for up to 96 h, with values ranging from 64-1024 μg mL−1. The in silico study with the chemical compounds of this species showed fungal inhibition potential of sterol-14-α-demethylase, highlighting 1-hydroxy-3,7-dimethoxyxanthone, which presented an affinity energy of -8.8 kcal mol−1, greater than that observed for fluconazole (−8.3 kcal mol−1). The fatty acids interacted with the active site of the enzyme but presented energies ≥ −7.4 kcal mol−1. Compounds isolated from this species have pharmacokinetic potential for the development of pharmaceutical formulations. Willd family Brazil extracts chromatographymass chromatography mass chromatographyflame flame 36.55 3655 36 55 (36.5 g−1, g1 g g−1 , 1 3.66 366 3 66 (3.6 108.82 10882 108 82 (108.8 7.86 786 7 86 (7.8 41.11 4111 41 11 (41.1 dihomoγlinolenic dihomo γ linolenic 85.48 8548 85 48 (85.4 209.00 20900 209 00 (209.0 1hydroxy3,7dimethoxyxanthone 1hydroxy37dimethoxyxanthone hydroxydimethoxyxanthone hydroxy 3,7 dimethoxyxanthone identified Candida Sporothrix 9 h 641024 64 1024 64-102 mL1 mL mL−1 sterol14αdemethylase, sterol14αdemethylase sterolαdemethylase sterol 14 α demethylase, demethylase sterol-14-α-demethylase 1hydroxy3,7dimethoxyxanthone, dimethoxyxanthone, 8.8 88 8 -8. mol1 mol mol−1 −8.3 83 (−8. . mol−1) 74 4 −7. formulations 36.5 365 5 (36. g− 3.6 6 (3. 108.8 1088 10 (108. 7.8 78 (7. 41.1 411 (41. 85.4 854 (85. 209.0 2090 20 0 (209. 1hydroxy3 7dimethoxyxanthone 37 3, 64102 102 64-10 mL− αdemethylase 8. -8 mol− −8. (−8 −7 36. (36 3. (3 108. (108 7. (7 41. (41 85. (85 209. 2 (209 1hydroxy 6410 64-1 - −8 (− − ( (10 (4 (8 (20 641 64- (1 (2

Lisdexamfetamine is a prodrug that is converted to d-amphetamine in the body, mainly used to treat attention deficit hyperactivity disorder in children and adults. Its mechanism involves the enhancement of neurotransmitters such as norepinephrine and dopamine, which are critical for attention and behavioral regulation. With the upcoming patent expiration of Vyvanse®, bioanalytical methods for the quantification of lisdexamfetamine in plasma are needed for use in pharmacokinetic studies. In this work, we developed and validated a sensitive bioanalytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for lisdexamfetamine quantification in human plasma. The method developed was performed for 4 min per sample and using the concentration range of 0.3-100 ng mL-1. Intra-batch, inter-batch and instrument reproducibility, the precision was lower than 10%. The results demonstrated that the method is rapid, sensitive, robust, and suitable for pharmacokinetic studies. damphetamine d amphetamine body adults dopamine regulation Vyvanse Vyvanse® studies work chromatographytandem chromatography tandem LCMS/MS LCMSMS LC MS/MS MS (LC-MS/MS 0.3100 03100 0.3 100 0 3 0.3-10 mL1. mL1 mL 1. 1 mL-1 Intrabatch, Intrabatch Intra batch, batch Intra-batch interbatch inter reproducibility 10 10% rapid robust LCMS MSMS 3100 0.310 0310 03 0. 0.3-1 mL- 310 0.31 031 0.3- 31

Compared to other species, components of Combretum lanceolatum are still with few data reported in the literature. This work describes the compounds identification, antioxidant and antimicrobial activities of C. lanceolatum twigs. Ethanolic extract (EECLT) from C. lanceolatum twigs was submitted to partition obtaining: hexane (HF), diethyl ether (EEF), ethyl acetate (EAF) and hydromethanolic (HMF) fractions. They were analyzed by gas chromatography-mass spectrometry, high performance liquid chromatography coupled to mass spectrometry and direct insertion mass spectrometry and evaluated for antioxidant assay (2,2-diphenyl-1-picrylhydrazyl (DPPH) method) and antimicrobial assay. Fifty-seven compounds were identified in the fractions. In antioxidant assay, EECLT and EAF demonstrated good antioxidant potential (half maximal effective concentration (EC50): 57.9 and 45.4 µg mL–1, respectively), better than the positive control butylated hydroxytoluene (BHT) (EC50: 69.34 µg mL–1). For antimicrobial assay, all fractions presented promising minimal inhibitory concentration (MIC). EECLT presented the best values against Staphylococcus aureus (125 µg mL–1) and Escherichia coli (62.5 µg mL–1) and better than the positive control fluconazole (8 and 16 µg mL–1) against Candida albicans (3.9 µg mL–1) and Candida krusei (15.6 µg mL–1) strains. This study presents relevant chemical and biological information about C. lanceloatum expanding the knowledge of Brazilian flora. species literature identification C (EECLT obtaining HF, HF , (HF) EEF, EEF (EEF) (EAF HMF (HMF chromatographymass 2,2diphenyl1picrylhydrazyl 22diphenyl1picrylhydrazyl diphenylpicrylhydrazyl 2,2 diphenyl 1 picrylhydrazyl 2 DPPH (DPPH method Fiftyseven Fifty seven half EC50 EC (EC50) 579 57 9 57. 454 45 4 45. mL1 mL mL–1 respectively, respectively respectively) BHT (BHT (EC50 6934 69 34 69.3 mL–1. . MIC. MIC (MIC) 125 (12 62.5 625 62 5 (62. 8 ( 3.9 39 3 (3. 15.6 156 15 6 (15. strains flora (HF (EEF 2diphenyl1picrylhydrazyl 22 2, EC5 mL– (EC5 693 69. (MIC 12 (1 62. (62 3. (3 15. (15 (EC (6

A new alkaloid, named brazoide Ε (6), three known steroids (campesterol, β-sitosterol, stigmasterol), two glucosides (3-O-β-D-glucopyranosylsitosterol and 3-O-β-D-glucopyranosyl stigmasterol) and sucrose were isolated from the leaves and stems of Justicia wasshauseniana. Their structures were characterized using high-resolution electrospray ionization mass spectrometry (HRESIMS), nuclear magnetic resonance (1D and 2D NMR), and infrared (IR) spectroscopy. To reinforce the structural proposal, an acetylated derivative (6a) was obtained and its data compared to 6. Moreover, circular dichroism spectroscopy (CD) analysis was performed to determine the absolute stereochemistry, time-dependent density functional theory (TD-DFT) at the wB97X-D/def2-TZVP level, adopting functionals M06-2X and wB97X-D and base aug-cc-pVDZ, was employed to confirm the CD analysis. alkaloid 6, 6 , (6) campesterol, campesterol (campesterol βsitosterol, βsitosterol β sitosterol, sitosterol β-sitosterol stigmasterol, stigmasterol 3OβDglucopyranosylsitosterol OβDglucopyranosylsitosterol 3 O D glucopyranosylsitosterol 3OβDglucopyranosyl OβDglucopyranosyl glucopyranosyl wasshauseniana highresolution high resolution HRESIMS, HRESIMS (HRESIMS) 1D NMR, NMR NMR) IR (IR proposal 6a a (6a Moreover (CD stereochemistry timedependent time dependent TDDFT TD DFT (TD-DFT wB97XD/def2TZVP wB97XDdef2TZVP wBXDdefTZVP wB97X D/def2 TZVP def2 wB X def level M062X MX M06 2X M wB97XD wBXD augccpVDZ, augccpVDZ aug cc pVDZ, pVDZ aug-cc-pVDZ (6 (HRESIMS def2TZVP XD XDdef wBX Ddef2 Ddef D/def M0 ( defTZVP

Methods used to determine pesticide residues in teas typically require several laborious steps for sample preparation before analysis. In this study, a simple method based on solid-liquid extraction with low-temperature partitioning (SLE/LTP) and analysis by gas chromatography coupled to mass spectrometry (GC-MS) was optimized and validated for the determination of pesticide residues (pirimiphos-methyl, flutriafol, cyproconazole, and bifenthrin) in dehydrated green tea leaves. After low-temperature partitioning (LTP), the extract in acetonitrile was subjected to a clean-up step using primary secondary amine (PSA) and octadecylsilane (C18) as sorbents for chlorophyll removal. The optimized SLE/LTP-GC-MS method was validated, and it proved to be effective and selective for extracting pesticides from green tea samples, presenting limit of detection (LOD) and limit of quantification (LOQ) of 0.015 and 0.050 mg kg-1, respectively. Recovery ranged between 81-111%, coefficients of variation were less than 16% and coefficients of determination (R2) were greater than 0.990. The optimized and validated method was applied to green tea and 13 other tea varieties sampled in South and Southeast regions of Brazil. The pesticides under study were detected in some of those samples at values higher than the maximum residue limits (MRLs) allowed by the European Union. solidliquid solid liquid lowtemperature low temperature SLE/LTP SLELTP SLE LTP (SLE/LTP GCMS GC MS (GC-MS pirimiphosmethyl, pirimiphosmethyl pirimiphos methyl, methyl (pirimiphos-methyl flutriafol cyproconazole bifenthrin leaves LTP, , (LTP) cleanup clean up PSA (PSA C18 C (C18 removal SLE/LTPGCMS SLELTPGCMS LOD (LOD LOQ (LOQ 0015 0 015 0.01 0050 050 0.05 kg1, kg1 kg 1, 1 kg-1 respectively 81111%, 81111 81 111%, 111 81-111% 16 R2 R (R2 0990 990 0.990 Brazil MRLs (MRLs Union (LTP C1 (C1 LTPGCMS 001 01 0.0 005 05 kg- 81111% 8111 8 111% 11 81-111 (R 099 99 0.99 (C 00 0. 811 81-11 09 9 0.9 81-1 81-

Gas chromatography coupled to mass spectrometry (GC-MS) has been widely used, and along with other methodologies such as derivatization, is a powerful tool to analyze phytocompounds, including cuticular wax components. The loss of structural information upon fragmentation of waxes makes it difficult to interpret and identify the GC-MS mass spectra of these compounds with the traditional methods, as digital libraries. Therefore, as a new complementary alternative to traditional methods of identifying aliphatic acyclic lipids based on mass spectra, we present the new software WaxAlly in this technical note. WaxAlly is a new software created based on simple algorithms, enabling the rapid recognition by the user of eight aliphatic acyclic lipid classes, including alkanes, alkenes, aldehydes, ketones, esters, and TMS derivatives of free fatty acids, primary and secondary alcohols, and their homologues with carbon chains varying between 10 and 100 carbons. Additionally, the WaxAlly software provides a section for data organization, internet comparison to NIST and PubChem databases, and academic information about mass fragmentation of acyclic lipids. The software has proven to be a very useful complementary technique in identifying plant wax lipid homologues, and new fragmentation patterns of lipid classes can be added in the future to improve the program. GCMS GC MS (GC-MS used derivatization phytocompounds components libraries Therefore note algorithms alkanes alkenes aldehydes ketones esters acids alcohols 1 carbons Additionally organization databases program

The present study analyzed the chemical composition and phytotoxic activity of Artemisia lancea essential oil (EO). Gas chromatography-mass spectrometry (GC-MS) results showed the presence of 55 compounds, representing 82.36% of the entire EO, with eucalyptol (18.7%) being the most abundant constituent. Phytotoxic bioassay results indicated that the EO (concentration ranging from 0.25-5 mg mL−1) inhibited the growth of Amaranthus retroflexus and Setaria viridis. Root length of A. retroflexus and S. viridis were reduced with the increasing concentration of the EO, especially when the EO was applied at 1-5 mg mL−1. When treated with 1-5 mg mL−1 EO, shoot length of A. retroflexus and S. viridis were also significantly suppressed. The half maximal inhibitory concentration (IC50) values for inhibiting root and shoot growth of A. retroflexus by the EO were 0.284 and 0.246 mg mL−1; for S. viridis, the EO showed IC50 values of 0.44 and 0.262 mg mL−1 for root and shoot inhibition, respectively. The most promising findings were observed when A. lancea EO concentration reached 1 mg mL−1 and higher, which completely inhibited seed germination of A. retroflexus and S. viridis. These findings suggest A. lancea EO has potential as an eco-friendly bioherbicide for agricultural weed control. EO. . (EO) chromatographymass chromatography mass GCMS GC MS (GC-MS 5 compounds 8236 82 36 82.36 18.7% 187 18 7 (18.7% constituent 0.255 0255 0.25 0 25 0.25- mL1 mL A S 15 1- mL− suppressed IC (IC50 0284 284 0.28 0246 246 0.24 IC5 044 44 0.4 0262 262 0.26 inhibition respectively higher ecofriendly eco friendly control (EO 823 8 3 82.3 18.7 (18.7 255 025 0.2 2 (IC5 028 28 024 24 04 4 0. 026 26 82. 18. (18. 02 (IC (18 (1 (