Precursor Compounds Research Articles

Impact of biological wastewater treatment on the reactivity of N-Nitrosodimethylamine precursors

N-Nitrosodimethylamine (NDMA) is a probable human carcinogen which forms during chloramination of wastewater-impacted drinking waters. Municipal wastewater effluents are considered as major sources of NDMA precursors affecting downstream water quality. To evaluate the deactivation mechanisms and efficiencies of NDMA precursors during secondary treatment with the activated sludge (AS) process, NDMA formation potentials (FPs) of selected model precursor compounds and sewage components (i.e., blackwaters and greywaters) were monitored in batch AS treatment tests. After 24-h incubation with four different types of AS (i.e., domestic rural, domestic urban, textile and lab-grown AS), NDMA FP of trimethylamine (TMA) and minocycline (MNCL) decreased by 77-100%, while there was only 29-46% reduction in NDMA FP of sumatriptan (SMTR). The reduction in NDMA FP associated with ranitidine (RNTD) varied between 34% and 87%. The decrease in NDMA FP of RNTD depended on the AS type, hydraulic retention time (HRT) and solids retention time (SRT). The domestic AS (rural and urban) achieved higher decreases in NDMA FPs of the tested model precursors than the textile AS or lab-grown AS. Increasing the HRT or SRT enhanced NDMA FP decrease for RNTD. Among different processes tested (i.e., biodegradation, biosorption and volatilization), biosorption was the major mechanism responsible for the NDMA FP decrease of RNTD, MNCL and SMTR, while biodegradation was the major NDMA FP reduction mechanism for TMA. The reduction in NDMA FP of RNTD via biodegradation depended on the AS activity which may vary with sampling seasons and SRT. NDMA FPs in all tested sewage components (i.e., blackwaters and greywaters) decreased after 24-h AS treatment. Urine in blackwater was the predominant (i.e., >90%) contributor to NDMA FP in domestic sewage and AS-treated effluents.

Thin SiNC/SiOC Coatings with a Gradient of Refractive Index Deposited from Organosilicon Precursor

In this work, optical coatings with a gradient of the refractive index are described. Its aim was to deposit, using the RF PECVD method, films of variable composition (ranging from silicon carbon-oxide to silicon carbon-nitride) for a smooth change of their optical properties enabling a production of the filter with a refractive index gradient. For that purpose, two organosilicon compounds, namely tetramethyldisilazane and hexamethyldisilazane, were selected as precursor compounds. The results reveal better optical properties of the materials obtained from the latter source. Depending on whether deposited in pure oxygen atmosphere or under conditions of pure nitrogen, the refractive index of the coatings amounted to 1.65 and to 2.22, respectively. By using a variable composition N2/O2 gas mixture, coatings of intermediate magnitudes of “n” were acquired. The optical properties were investigated using both UV-Vis absorption spectroscopy and variable angle spectroscopic ellipsometry. The chemical structure of the coatings was studied with the help of Fourier transform infrared and X-ray photoelectron spectroscopies. Finally, atomic force microscopy was applied to examine their surface topography. As the last step, a “cold mirror” type interference filter with a gradient of refractive index was designed and manufactured.

Cryptotanshinone ameliorates the pathogenicity of Streptococcus suis by targeting suilysin and inflammation.

Streptococcus suis is a highly zoonotic pathogen that is a serious threat to human health and the development of the pig industry worldwide. The virulence factors produced during S. suis infection play an important role, and the pore-forming activity of suilysin is considered an important virulence-related factor, especially in meningitis. Treatment of S. suis infection with traditional antibiotics is becoming increasingly challenging due to bacterial resistance. The purpose of this study is to verify the role of cryptotanshinone in the process of S. suis infection and provide a new drug precursor for the treatment of S. suis infection. In this study, we used circular dichroism spectroscopy to demonstrate that cryptotanshinone alters the secondary structure of suilysin. The results of the antibacterial activity and haemolysis assays showed cryptotanshinone could inhibit the pore-forming activity of suilysin without affecting bacterial growth or its expression. We also showed that cryptotanshinone reduces bacterial damage and penetration in vitro, reduce the S. suis-induced inflammatory response and provide protection against bacterial infections in vivo and in vitro. Cryptotanshinone is a potential compound precursor for treating S. suis infection. Cryptotanshinone may be a promising leading compound for S. suis infection and related diseases.

Mutagenesis, breeding, and characterization of sake yeast strains with low production of dimethyl trisulfide precursor

Dimethyl trisulfide (DMTS) is one of the main components responsible for hineka, the aroma associated with deteriorated Japanese sake during storage. The molecule 1,2-dihydroxy-5-(methylsulfinyl)pentan-3-one (DMTS-P1) has been previously identified as a major precursor compound of DMTS. Furthermore, it had been suggested that the yeast methionine salvage pathway is involved in the production of DMTS-P1. In sake brewing tests, DMTS-P1 and the DMTS producing potential (DMTS-pp; DMTS amount of sake after accelerated storage) were significantly reduced in mde1 or mri1 strain, which lack genes of the methionine salvage pathway. Industrial use of the gene-disrupting strains may not be accepted in the Japanese food industry. In order to obtain mde1 or mri1 mutants, we established a method to screen 5'-methylthioadenosine (MTA) non-utilizing strains using minimum culture medium containing methionine or MTA by ethyl methanesulfonate (EMS) mutagenesis with methionine-auxotrophic sake yeast haploid. As expected, mde1 and mri1 mutants were identified among the obtained mutants by an established screening method. The obtained strains had poor fermentation ability in sake brewing tests, so back-crossing was performed on the mutants to obtain mde1 or mri1 homozygous mutants. These strains had improved brewing characteristics, and DMTS-P1 and the DMTS-pp of the produced sake were significantly lower than those of the parent strains. These strains are expected to contribute to improving the maintenance of sake quality during storage.

Improved and Flexible Synthetic Access to the Spiroindole Backbone of Cebranopadol.

By changing the dimethylamino to a nitro group, a novel synthetic access to the spirocyclic opioid analgesic cebranopadol was developed that is much more efficient compared with the established route. On the basis of the α-acidity of α-nitrotoluene, the two-fold Michael addition to acrylate gave an acyclic precursor compound, which was easily transformed by Dieckmann condensation and decarboxylation to the cyclohexanone derivative needed for the annulation of the indole ring by an oxa-Pictet-Spengler reaction. As an additional benefit, the reduction of the nitro group furnished an amine, which could be late-stage-diversified to carboxamides, sulfonamides, ureas, and N-alkyl congeners. The transformation of the nitro group at the spirocyclic scaffold to the dimethylamino function of the actual title compound was achieved in one step with zinc/formic acid/formaldehyde in 83% yield.

A reaction-based ratiometric fluorescent probe for mercury ion detection in aqueous solution.

Mercury ions are crucially harmful to ecosystem and human being due to their characters of bioaccumulation and difficulty of biochemical degradation. Therefore, development of mercury ion detection methods has attracted increasing interests recently. In this study, we successfully synthesized a hydroxyphenylbenzothiazole (HBT)-based fluorescent probe HBT-Hg in an extremely simple manner for mercuric ions detection. The spectral studies revealed that the probe HBT-Hg could react with Hg2+ selectively and sensitively in PBS buffer (10mM, pH=7.40), showing ratiometric fluorescent changes from blue to light green. The response mechanism of the probe HBT-Hg and Hg2+ was finally confirmed by HPLC analysis, viz., the probe HBT-Hg converted to its precursor compound 1. Finally, the probe HBT-Hg was successfully applied in monitoring Hg2+ in living A549 cells.

Reforming of toluene with simulated automobile exhaust gas over hydrotalcite-like-compound-derived Ni catalyst

Reforming of toluene, which is a model compound of gasoline, with model exhaust gas (model EGR gas) of gasoline engine was carried out with Ni catalyst. The Ni/Mg/Al catalyst prepared from hydrotalcite-like precursor compound showed higher performance than Ni/α-Al2O3 catalyst in terms of activity, stability and coke deposition resistance. The activity of Ni/Mg/Al after the initial deactivation was about 1/200 of Rh/CeO2 based on the weight of active metal (Ni or Rh), and the difference was much smaller than that of price between Ni and Rh. The amount of coke deposition on Ni/Mg/Al catalyst was increased with increases of W/F or partial pressure of toluene, especially at the outlet of the catalyst bed, where the coke formation is mainly due to CO disproportionation. The deactivation was also severer in larger partial pressure of toluene when the toluene feed was changed while partial pressure of H2O, N2 and CO2 was set constant to the model EGR gas. Large steady state H2 formation and high conversion were obtained at conditions with low partial pressure of toluene, similarly to the case of simple steam reforming, the Ni/Mg/Al catalyst after reaction can be regenerated by the combination of oxidation (at 773 K) and reduction (at 1073 K) treatments. The effect of feed ratio of H2O:N2:CO2 showed that low partial pressure of steam in model EGR gas in comparison with standard feed gas for steam reforming is the main reason for low toluene conversion and coke deposition resistance. On the other hand, the presence of CO2 did not affect the conversion and the coke deposition behavior so significantly.

An investigation on the pyrolysis of the main residue of the brewing industry

Brewer's spent grain (BSG) is the main by-product of the brewing industry. In this work, the pyrolysis of BSG using a fixed bed reactor was studied with respect to the valorization of this residue. The effects of the heating rate (10-50 °C/min) and temperature (450-650 °C) on the yields of pyrolysis products and on the physicochemical properties of the main products were quantified. The highest liquid yield (60.7%) was obtained at the pyrolysis temperature of 650 °C with a heating rate of 30 °C/min. The highest char yield (29.3%) was obtained at 550 °C and at heating rate of 10 °C/min. The results showed that high heating rates suppress dehydration reactions and favor bio-oil production. The produced biochar showed good potential for fuel application due to its high heating value (HHV) (27.1–28.3 kJ/g), moderate ash content (11.5%) and low sulfur content (<0.6%). The produced bio-oil contained phenols and ketones, which are precursors of several compounds used in the chemical industry, as well as pyrazines that are used in the pharmaceutical industry.

MOF-derived Co3O4 microspheres with pagoda cauliflower shape as anode materials for stable life Li-ion battery

Metal organic frameworks (MOFs) are widely used in the synthesis of metal oxides as important organic–inorganic compound precursors. A perovskite ABO3-type Co-based MOF [NH4][Co(HCOO)3] was synthesized from a simple mixture without any adjuvant. Porous Co3O4 microspheres are used as anode materials for lithium-ion batteries (LIBs), which are obtained from [NH4][Co(HCOO)3] as a precursor through a pyrolysis process in air. The obtained pagoda cauliflower-shaped Co3O4 microspheres exhibit an excellent electrochemical performance.

Room‐Temperature Formation Pathway for CdTeSe Alloy Magic‐Size Clusters

AbstractLittle is known about the pathway of room‐temperature formation of ternary CdTeSe magic‐size clusters (MSCs) obtained by mixing binary CdTe and CdSe induction period samples containing binary precursor compounds (PCs) of MSCs, monomers (Ms), and fragments (Fs). Also, unestablished are dispersion effects that occur when as‐mixed samples (without incubation) are placed in toluene (Tol) and octylamine (OTA) mixtures. The resulting ternary MSCs, exhibiting a sharp optical absorption peak at 399 nm, are labelled CdTeSe MSC‐399, and their PCs are referred to as CdTeSe PC‐399. When the amount of OTA is relatively small, single‐ensemble MSC‐399 evolved without either binary CdTe or CdSe MSCs. When the OTA amount is relatively large, CdTe MSC‐371 appeared initially and then disappeared, while single‐ensemble MSC‐399 developed more deliberately. The larger the OTA amount, the more slowly these changes proceeded. The substitution reaction of CdTe PC + CdSe M/F↔CdTeSe PC‐399 + CdTe M/F is proposed to be rate‐determining for the MSC‐399 formation in a Tol and OTA mixture. This study provides further understanding of the transformation pathway between MSCs.

Room‐Temperature Formation Pathway for CdTeSe Alloy Magic‐Size Clusters

Little is known about the pathway of room-temperature formation of ternary CdTeSe magic-size clusters (MSCs) obtained by mixing binary CdTe and CdSe induction period samples containing binary precursor compounds (PCs) of MSCs, monomers (Ms), and fragments (Fs). Also, unestablished are dispersion effects that occur when as-mixed samples (without incubation) are placed in toluene (Tol) and octylamine (OTA) mixtures. The resulting ternary MSCs, exhibiting a sharp optical absorption peak at 399 nm, are labelled CdTeSe MSC-399, and their PCs are referred to as CdTeSe PC-399. When the amount of OTA is relatively small, single-ensemble MSC-399 evolved without either binary CdTe or CdSe MSCs. When the OTA amount is relatively large, CdTe MSC-371 appeared initially and then disappeared, while single-ensemble MSC-399 developed more deliberately. The larger the OTA amount, the more slowly these changes proceeded. The substitution reaction of CdTe PC + CdSe M/F↔CdTeSe PC-399 + CdTe M/F is proposed to be rate-determining for the MSC-399 formation in a Tol and OTA mixture. This study provides further understanding of the transformation pathway between MSCs.

Development of a biocatalytic cascade for synthesis of 2-oxo-4-(hydroxymethylphosphinyl) butyric acid in one pot

2-Oxo-4-(hydroxymethylphosphinyl) butyric acid (PPO) is an important precursor compound for the broad-spectrum herbicide l-glufosinate (L-PPT). In this study, the gene of d-amino acid oxidase (DAAO) was cloned and expressed in Escherichia coli. By coupling exogenous catalase (CAT), a biocatalytic cascade was constructed for synthesis of PPO in one pot. The bioprocess was optimized on a 300 mL scale reaction by one factor at a time optimization. The conversion of this biocatalytic cascade achieved 46.8% towards 400 mM DL-PPT within 4 h. These results indicated that DAAO could be applied to the large-scale bioproduction of PPO and provide a promising route for the asymmetric synthesis of L-PPT by bio-enzymatic methods using PPO as the substrate.

Brazilian artisanal cheeses are rich and diverse sources of nonstarter lactic acid bacteria regarding technological, biopreservative, and safety properties—Insights through multivariate analysis

In this study a total of 220 isolates of lactic acid bacteria (LAB) recovered from 10 types of Brazilian artisanal cheeses marketed in 4 main regions of Brazil were evaluated regarding their safety and ability to produce diacetyl (a precursor of aromatic compounds), exopolysaccharides (EPS; from different sugar sources), and antagonistic activity against Listeria monocytogenes and Staphylococcus aureus. The results indicated that 131 isolates (59.6%) were classified as strong (40.5%) and moderate (19.1%) diacetyl producers; 28 isolates (12.7%) stood out due to their remarkable production of EPS from different sugars, including sucrose (3.2%), fructose (2.3%), lactose (2.3%), and glucose (6%). Furthermore, 94.1% and 95.9% of isolates presented antagonistic activity against S. aureus and L. monocytogenes, respectively, even though only 27 isolates (12.3%) exhibited positive results in the bacteriocin production test. None of the isolates tested presented hemolytic activity, and 117 were classified as safe, due to their intrinsic resistance to a maximum of 4 different antibiotics. The data obtained for assessment of antibiogram profile and technological potential (moderate and high production of diacetyl, EPS, and bacteriocins) were submitted to a multiple correspondence analysis to correlate them with the cheese of isolation. Regarding the antimicrobial profile of LAB strains, it was possible to verify an association between isolates from Minas artisanal cheeses from Araxá and resistance to tetracycline; Minas artisanal cheeses from Serro and resistance to erythromycin; Coalho and Minas artisanal cheese from Cerrado and resistance to penicillin; and isolates from Serrano and Colonial cheeses with clindamycin and ceftazidime resistance. Although the susceptibility of strains to these antibiotics was considered high (71.8-80.5%), these data may be related to the horizontal transfer of genes in the production chain of these cheeses. Results of multiple correspondence analysis also showed that isolates with antagonistic activity were mostly isolated from Manteiga, Colonial, and Coalho cheeses. The isolates with high or moderate EPS-producer ability from sucrose, glucose, and fructose were mainly associated with Minas artisanal cheeses from Cerrado. In contrast, isolates with high or moderate EPS-producer ability from lactose were isolated from Serrano, Minas artisanal cheeses from Canastra, and Campo das Vertentes microregions. Finally, isolates from Minas artisanal cheeses (from Araxá microregion), Coalho, and Caipira cheeses were associated with moderate/high diacetyl production. To the best of the authors' knowledge, this study provides, for the first time, data indicating that the dominant technological, biopreservative, and safety properties of LAB isolates can be correlated with the type of Brazilian artisanal cheeses, which denotes its singularity. This knowledge is of utmost relevance for the development of starter or adjunct cultures with tailored properties.

Rhenium oxide nanoparticles – Sonochemical synthesis and integration on anode powders for solid oxide fuel cells

Rhenium oxide nanoparticles have been prepared using ultrasonication at 20 kHz. Samples characterization was committed via SEM-EDX, TEM, XRD, and Raman spectroscopy. Various experimental parameters were examined, including precursor/substrate amounts, ultrasonication intensity, and type of solvent used. Insights to the agglomeration of the prepared nanoparticles depending on the preparation parameters are given. As ultrasonic source we used either an ultrasonic probe by Sonics & Materials Inc. (20 kHz, 750 W net output) or a Bandelin SONOPULS HD 3200 ultrasound generator (20 kHz, 200 W net output) at intensities between 30 and 100 W/cm2. The rhenium oxide nanoparticles haven been decorated on state-of-the-art anode materials (NiO/GDC) for solid oxide fuel cells (SOFCs) in order to prepare catalytically more active anode powders. These experiments revealed that ultrasonication intensity and solvents used are able to affect final nanoparticles size distribution and morphology. At the same time, ratio of precursor and substrate compounds amounts as well as ultrasonication intensity and duration were all found to affect the decoration loading extend of nanoformations on substrate powders. The results showing the influence of the above-mentioned parameters allowed for the quantification of the effects on the loading and the preferable sites of the decoration.

Moisture-activated release of hexanal from imidazolidine precursor encapsulated in ethylcellulose/poly(ethylene oxide) nonwoven for shelf-life extension of papaya

Abstract Hexanal extends the shelf life of fresh produce. Due to its high volatility and spontaneous oxidation, control release of hexanal is a challenge. The objective of the study was to stabilize and encapsulate hexanal as an acid labile precursor in polymeric nonwovens and trigger its release in moisture environments in packaged fresh produce. Bilayer nonwovens were prepared by encapsulating hexanal precursor and citric acid (CA) (1, 5, 10 % (w/w)) in a mixture of ethylcellulose/poly(ethylene oxide) polymers. The hexanal (10 % (w/w)) was stabilized by forming a precursor compound via condensation with N,N’-dibenzylethane-1,2-diamine through a Schiff base reaction. The release of the hexanal from the nonwovens was studied at 0, 75 and 100 % relative humidity (RH) using gas chromatography. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed the presence of CA and hexanal in the nonwovens. The highest hexanal release was attained in the 10 % (w/w) CA nonwovens under 75 % RH after 6 h of study. The efficacy of the encapsulated hexanal precursor nonwovens containing 10 % (w/w) CA to delay the ripening of papaya fruits stored at 22 ± 1.5 °C was assessed during a 14-day storage period. The shelf life of papaya fruits was extended for 4 days relative to the control samples. The hexanal treated samples significantly (p

Synthesis and Characterization of a Magnesium Boryl and a Beryllium-Substituted Diazaborole.

Reaction of a lithium boryl, [(THF)2 Li{B(DAB)}] (DAB=[(DipNCH)2 ]2- , Dip=2,6-diisopropylphenyl), with a dinuclear magnesium(I) compound [{(Mes Nacnac)Mg}2 ] (Mes Nacnac=[HC(MeCNMes)2 ]- , Mes=mesityl) unexpectedly afforded a rare example of a terminal magnesium boryl species, [(Mes Nacnac)(THF)Mg{B(DAB)}]. Attempts to prepare the magnesium boryl via a salt metathesis reaction between the lithium boryl and a β-diketiminato magnesium iodide compound, instead led to an intractable mixture of products. Similarly, reaction of the lithium boryl with a β-diketiminato beryllium bromide precursor, [(Dep Nacnac)BeBr] (Dep=2,6-diethylphenyl) did not give a beryllium boryl, but instead afforded an unprecedented example of a beryllium substituted diazaborole heterocycle, [{(Dep Nacnac)Be(4-DAB-H )}BBr]. For sake of comparison, the same group 2 halide precursor compounds were treated with a potassium gallyl analogue of the lithium boryl, viz. [(tmeda)K{:Ga(DAB)}] (tmeda=N,N,N',N'-tetramethylethylenediamine), but no reactions were observed.

Investigating biological nitrogen cycling in lacustrine systems by FT-ICR-MS analysis of nitrogen-containing compounds in petroleum

Biological nitrogen cycling plays an important role in bio, environmental and petroleum geochemistry. Until now most research has focused on marine environments using nitrogen isotopes, and in contrast, nitrogen cycling in lacustrine environments remains poorly understood. To fill this knowledge gap, we present a case study of crude oils from Permian brackish and saline alkaline lacustrine rocks in the Junggar Basin, northwestern China. To complement the large variation in nitrogen isotope values in lacustrine sediments, we analyzed the pyrrolic N-containing compounds of crude oil using negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS). Our results show that pyrrolic compounds derived from biological sources are more abundant in oils from brackish lacustrine settings (i.e., the Jimusar Sag oils of the Junggar Basin) than in oils from alkaline lacustrine settings (i.e., the Mahu Sag oils of the Junggar Basin), which is mainly due to greater higher plant contributions to the latter. Higher plants provide abundant alkaloids and chlorophyll that are the biological precursors of pyrrolic N-containing compounds. In addition, anoxic, sulfate-type, brackish lacustrine settings provide abundant ferrous iron and sulfide that promote N fixation. This study provides the first insights into biological N cycling in brackish and alkaline lacustrine systems, which has significance for fossil fuel resources and their environmental impacts. Our data suggest that the N cycling in lacustrine systems might have an important role in entire Earth system N budget.

Synthesis and Fundamental Evaluation of Radioiodinated Rociletinib (CO-1686) as a Probe to Lung Cancer with L858R/T790M Mutations of Epidermal Growth Factor Receptor (EGFR).

Rociletinib (CO-1686), a 2,4-diaminopyrimidine derivative, is a highly potent tyrosine kinase inhibitor (TKI) that acts on epidermal growth factor receptor (EGFR) with L858R/T790M mutations. We supposed radioiodinated CO-1686 would function as a useful tool for monitoring EGFR L858R/T790M mutations. To aid in patient selection before therapy with EGFR-TKIs, this study aimed to develop a 125I-labeled derivative of CO-1686, N-{3-[(2-{[4-(4-acetylpiperazin-1-yl)-2-methoxyphenyl]amino}-5-(trifluoromethyl)pyrimidine-4-yl] amino}-5-([125I]iodophenyl)acrylamide ([125I]ICO1686) and evaluate its selectivity toward EGFR L858R/T790M. Radiosynthesis was performed by iododestannylation of the corresponding tributylstannyl precursor with [125I]NaI and N-chlorosuccinimide. The selectivity of the tracer for detecting EGFR L858R/T790M was evaluated using three relevant non-small cell lung cancer (NSCLC) cell lines—H1975, H3255 and H441 overexpressing the dual mutation EGFR L858R/T790M, active mutant EGFR L858R and wild-type EGFR, respectively. The nonradioactive ICO1686 and the precursor compound were successfully synthesized. A novel radiolabeled probe, [125I]ICO1686, was prepared with high radiochemical yield (77%) and purity (>99%). ICO1686 exhibited high cytotoxicity toward H1975 (IC50 0.20 ± 0.05 μM) and H3255 (IC50 0.50 ± 0.21 μM), which is comparable to that of CO-1686. In contrast, the cytotoxicity of ICO1686 toward H441 was 10-fold lower than that toward H1975. In the cell uptake study, the radioactivity uptake of [125I]ICO1686 in H1975 was 101.52% dose/mg, whereas the uptakes in H3255 and H441 were 33.52 and 8.95% dose/mg, respectively. The uptake of [125I]ICO1686 in H1975 was greatly reduced to 45.61% dose/mg protein by treatment with excess CO-1686. In vivo biodistribution study of the radiotracer found that its accumulation in H1975 tumor (1.77 ± 0.43% ID/g) was comparable to that in H3255 tumor (1.63 ± 0.23% ID/g) and the accumulation in H1975 tumor was not reduced by pretreatment with an excess dose of CO-1686. Although this radiotracer exhibited highly specific in vitro uptake in target cancer cells, structural modification is required to improve in vivo biodistribution.

Genome-wide identification and comparative analysis of GST gene family in apple (Malus domestica) and their expressions under ALA treatment.

Anthocyanins, a subclass of flavonoids, are synthesized at the cytoplasmic surface of the endoplasmic reticulum (ER), which then accumulate in vacuoles. Plant glutathione S-transferase (GST) genes are involved in anthocyanin transportation. Here, a total of 52, 42, 50, and 29 GST genes were identified from apple, pear, peach, and strawberry, respectively, through a comprehensive genome-wide survey. Based on phylogenetic analyses, the GST proteins of the four crops could be divided into the classes Phi, Tau, DHAR, TCHQD, and Lambda. The structure and chromosomal distribution of apple GST genes were further analyzed. The GST gene family expansion in apple likely occurred through tandem duplications, and purifying selection played a pivotal role in the evolution of GST genes. Synteny analysis showed strong microsynteny between apple and Arabidopsis/strawberry, but no microsynteny was detected between apple/strawberry/Arabidopsis and rice. Aminolevulinic acid (ALA), a key precursor of tetrapyrrole compounds, can significantly improve anthocyanin accumulation in fruits, Using RNA-seq and qRT-PCR analysis, we found that ALA treatment led to the differential expression of GST genes in apples. MdGSTF12 was strongly induced by ALA, suggesting that MdGSTF12 may play a role in ALA-induced anthocyanin accumulation. These results provide a detailed overview of GST genes in four Rosaceae species and indicate that GSTs are involved in ALA-induced anthocyanin accumulation.

Fermentation of Sauvignon blanc grape marc extract yields important wine aroma 3-sulfanylhexan-1-ol (3SH)

Grape marc, comprised of grape stems, seeds and skins, is an underutilised and potentially problematic waste material produced by the wine industry in often overwhelming quantities. This work aims to showcase this abundant waste material, for the first time, as a potentially valuable technological tool for improving wine quality through the production of the aroma compound 3-sulfanylhexan-1-ol (3SH) during fermentation.A scaled-up eco-friendly solid-liquid extraction method, using 100% water, to extract thiol precursor compounds 3-S-cysteinylhexan-1-ol (Cys-3SH) and 3-S-glutathionylhexan-1-ol (GSH-3SH) from Sauvignon blanc grape marc was undertaken. Quantitation of the vacuum-dried crude extract dissolved in model wine, using liquid chromatography tandem mass spectrometry (LC-MS/MS), showed that the extract contained 1.9 μg Cys-3SH and 11.46 μg GSH-3SH per gram of grape marc extract. Addition of low (14.6 g L−1) and high (58.3 g L−1) quantities of grape marc extract to synthetic grape medium inoculated with a commercial wine yeast strain, yielded appreciable concentrations of 3SH in finished wines (average of 216 ng L−1 for the low addition and 1244 ng L−1 for the high addition). Interestingly, the grape marc extract was found to accelerate the fermentation rate of the yeast, rather than cause inhibition or toxicity.