Fermentation Characteristics of Fermented Milk with Streptococcus thermophilus CICC 6063 and Lactobacillus helveticus CICC 6064 and Volatile Compound Dynamic Profiles during Fermentation and Storage.

The lactic acid bacteria Streptococcus thermophilus and Lactobacillus helveticus are commonly used as starter cultures in dairy product production. This study aimed to investigate the characteristics of fermented milk using different ratios of these strains and analyze the changes in volatile compounds during fermentation and storage. A 10:1 ratio of Streptococcus thermophilus CICC 6063 to Lactobacillus helveticus CICC 6064 showed optimal fermentation time (4.2 h), viable cell count (9.64 log10 colony-forming units/mL), and sensory evaluation score (79.1 points). In total, 56 volatile compounds were identified and quantified by solid-phase microextraction and gas chromatography-mass spectrometry (SPME-GC-MS), including aldehydes, ketones, acids, alcohols, esters, and others. Among these, according to VIP analysis, 2,3-butanedione, acetoin, 2,3-pentanedione, hexanoic acid, acetic acid, acetaldehyde, and butanoic acid were identified as discriminatory volatile metabolites for distinguishing between different time points. Throughout the fermentation and storage process, the levels of 2,3-pentanedione and acetoin exhibited synergistic dynamics. These findings enhance our understanding of the chemical and molecular characteristics of milk fermented with Streptococcus thermophilus and Lactobacillus helveticus, providing a basis for improving the flavor and odor of dairy products during fermentation and storage.

Efficient Synthesis and HPLC-Based Characterization for Developing Vanadium-48-Labeled Vanadyl Acetylacetonate as a Novel Cancer Radiotracer for PET Imaging.

Bis(acetylacetonato)oxidovanadium(IV) [(VO(acac)2], generally known as vanadyl acetylacetonate, has been shown to be preferentially sequestered in malignant tissue. Vanadium-48 (48V) generated with a compact medical cyclotron has been used to label VO(acac)2 as a potential radiotracer in positron emission tomography (PET) imaging for the detection of cancer, but requires lengthy synthesis. Current literature protocols for the characterization of VO(acac)2 require macroscale quantities of reactants and solvents to identify products by color and to enable crystallization that are not readily adaptable to the needs of radiotracer synthesis. We present an improved method to produce vanadium-48-labeled VO(acac)2, [48V]VO(acac)2, and characterize it using high-performance liquid chromatography (HPLC) with radiation detection in combination with UV detection. The approach is suitable for radiotracer-level quantities of material. These methods are readily applicable for production of [48V]VO(acac)2. Preliminary results of preclinical, small-animal PET studies are presented.

Mechanisms of isomerization and hydration reactions of typical ß-diketone at the air-droplet interface.

Acetylacetone (AcAc) is a typical class of ß-diketones with broad industrial applications due to the property of the keto-enol isomers, but its isomerization and chemical reactions at the air-droplet interface are still unclear. Hence, using combined molecular dynamics and quantum chemistry methods, the heterogeneous chemistry of AcAc at the air-droplet interface was investigated, including the attraction of AcAc isomers by the droplets, the distribution of isomers at the air-droplet interface, and the hydration reactions of isomers at the air-droplet interface. The results reveal that the preferential orientation of two AcAc isomers (keto- and enol-AcAc) to accumulate and accommodate at the acidic air-droplet interface. The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the "water bridge" structure is destroyed by H3O+, especially for the isomerization from keto-AcAc to enol-AcAc. At the acidic air-droplet interface, the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration. Keto-diol is the dominant products to accumulate at the air-droplet interface, and excessive keto-diol can enter the droplet interior to engage in the oligomerization. The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface, which indirectly facilitate the uptake and formation of more keto-diol. Our results provide an insight into the heterogeneous chemistry of ß-diketones and their influence on the environment.

Ethyl vinyl ketone activates oxidative and calcium burst and CML8-ACA8 participates in calcium recovery in Arabidopsis leaves.

Plants produce ethyl vinyl ketone (evk) in response to biotic stress, but the evk's identification and downstream defense response remain unclear. In this paper, it is predicted by docking for the first time that evk can be recognized by RBOH protein and assist the electron transfer of RBOHD/RBOHF by binding to its FAD or NADPH binding site. Surface plasmon resonance (SPR) binding assay shows that evk indeed bind to RBOHD. Here, we show that evk treatment increased H2O2 and intracellular calcium concentrations in Arabidopsis thaliana mesophyll cells, as observed by confocal laser scanning microscopy and non-invasive micro-test technology, and that H2O2 signaling functioned upstream of Ca2+ signaling. Yeast two-hybrid, firefly luciferase complementation imaging, and in vitro pull-down assays demonstrated that the ACA8 (AUTOINHIBITED Ca2+-ATPASE, ISOFORM 8)-CML8 (CALMODULIN-LIKE 8) interaction promoted Ca2+ efflux to return Ca2+ levels to the resting state.

Unleashing the power of acetylacetone: Effective control of harmful cyanobacterial blooms with ecological safety.

Harmful algal blooms resulting from eutrophication pose a severe threat to human health. Acetylacetone (AA) has emerged as a potential chemical for combatting cyanobacterial blooms, but its real-world application remains limited. In this study, we conducted a 42-day evaluation of AA's effectiveness in controlling blooms in river water, with a focus on the interplay between ecological community structure, organism functional traits, and water quality. At a concentration of 0.2 mM, AA effectively suppressed the growth of Cyanobacteria (88 %), Bacteroidia (49 %), and Alphaproteobacteria (52 %), while promoting the abundance of Gammaproteobacteria (5.0 times) and Actinobacteria (7.2 times) that are associated with the degradation of organic matter. Notably, after dosing of AA, the OD680 (0.07 ± 0.02) and turbidity (8.6 ± 2.1) remained at a satisfactory level. AA induced significant disruptions in two photosynthesis and two biosynthesis pathways (P < 0.05), while simultaneously enriching eight pathways of xenobiotics biodegradation and metabolism. This enrichment facilitated the reduction of organic pollutants and supported improved water quality. Importantly, AA treatment decreased the abundance of two macrolide-related antibiotic resistance genes (ARGs), ereA and vatE, while slightly increased the abundance of two aminoglycoside-related ARGs, aacA and strB. Overall, our findings establish AA as an efficient and durable algicide with favorable ecological safety. Moreover, this work contributes to the development of effective strategies for maintaining and restoring the health and resilience of aquatic ecosystems impacted by harmful algal blooms.

[Risk factors for the development of psychotic disorders associated with synthetic cathinones usage]. / Faktory riska razvitiya psikhoticheskikh rasstroistv, svyazannykh s upotrebleniem sinteticheskikh katinonov.

OBJECTIVE: To identify risk factors and predictors of the development of psychotic disorders in patients who used synthetic cathinones (SKat). MATERIAL AND METHODS: The study included 176 patients who used SKat, which was toxicologically confirmed. One hundred and eleven (63.1%) were male and 65 (36.9%) were female. The median age was 27 years (22-32 (Q1-Q3)). Patients were divided into main and control groups depending on the presence of a psychotic disorder. The main group (those who developed psychosis) consisted of 98 patients, the control groupincluded 78 participants. Clinical-psychopathological, parametric and statistical methods were performed to study predictors and risk factors for the development of psychotic disorders associated with the use of SKat. RESULTS: The study established factors influencing the incidence of psychosis. Older patients were more likely to develop psychosis (p=0.002). Patients who used SKat for more than 21 consecutive days developed psychoses more often (p=0.048). The use of α-pvp (α-pyrrolidinovalerophenone, alpha-pvp) more often led to the development of psychosis (p<0.001). Patients undergoing rehabilitation were less likely to experience the development of psychosis (p=0.009). The resulting regression model is statistically significant (p<0.001). Based on the value of the Nigelkirk coefficient of determination, the model explains 30.9% of the observed group variance. It has been established that the combination of the following factors increases the chances of developing psychosis: female gender, age, duration of daily use, the presence of signs of mental infantilism, fear of the dark in childhood. In turn, the experience of undergoing rehabilitation and any pathology of the mother's pregnancy reduces the risk of psychosis. CONCLUSION: The results are consistent with other studies of substance-induced psychoses. The observed patterns demonstrate that this is a special group of disorders that requires the attention of specialists. The results allow us to outline the field for further study, and may also be useful in the development of therapeutic and preventive recommendations.

Unexpected Rearrangement Reactions of the 14-Aminonaltrexone Skeleton.

The reaction of 14-aminonaltrexone with acetic anhydride was found to produce a range of different novel compounds between the free compound and its hydrochloride. The hydrochloride produced a compound with an acetylacetone moiety, whereas the free form produced a compound with a pyranopyridine moiety. Efforts to isolate reaction intermediates and density functional theory calculations have elucidated those formation mechanisms with both bearing the novel morphinan-type skeleton. Furthermore, a derivative with the acetylacetone moiety showed binding to opioid receptors.

Untargeted metabolomics analysis assisted by signal selection for comprehensively identifying metabolites of new psychoactive substances: 4-MeO-α-PVP as an example.

New psychoactive substances (NPS) have been rapidly emerged as legal alternatives to controlled drugs, which raised severe public health issue. The detection and monitoring of its intake by complete metabolic profiling is an urgent and vital task. Untargeted metabolomics approach has been applied for several NPS metabolites studies. Although the number of such works is relatively limited but with a rapidly growing need. The present study aimed to propose a procedure that includes liquid chromatography high-resolution mass spectrometry (LC-HRMS) analysis and a signal selection software, MetaboFinder, programed as a web tool. The comprehensive metabolites profile of one kind of NPS, 4-methoxy-α-pyrrolidinovalerophenone (4-MeO-α-PVP), was studied by using this workflow. In this study, two different concentrations of 4-MeO-α-PVP along with as blank sample were incubated with human liver S9 fraction for the conversion to their metabolites and followed by LC-MS analysis. After retention time alignment and feature identification, 4640 features were obtained and submitted to statistical analysis for signal selection by using MetaboFinder. A total of 50 features were considered as 4-MeO-α-PVP metabolite candidates showing significant changes (p < 0.00001 and fold change >2) between the two investigated groups. Targeted LC-MS/MS analysis was conducted focusing on these significantly expressed features. Assisted by chemical formula determination according to high mass accuracy and in silico MS2 fragmentation prediction, 19 chemical structure identifications were achieved. Among which, 8 metabolites have been reported derived from 4-MeO-α-PVP in a previous literature while 11 novel 4-MeO-α-PVP metabolites were identified by using our strategy. Further in vivo animal experiment confirmed that 18 compounds were 4-MeO-α-PVP metabolites, which demonstrated the feasibility of our strategy for screening the 4-MeO-α-PVP metabolites. We anticipate that this procedure may support and facilitate traditional metabolism studies and potentially being applied for routine NPS metabolites screening.

Polypyridyl CoII -Curcumin Complexes as Photoactivated Anticancer and Antibacterial Agents.

Four new CoII complexes, [Co(bpy)2 (acac)]Cl (1), [Co(phen)2 (acac)]Cl (2), [Co(bpy)2 (cur)]Cl (3), [Co(phen)2 (cur)]Cl (4), where bpy=2,2'-bipyridine (1 and 3), phen=1,10-phenanthroline (2 and 4), acac=acetylacetonate (1 and 2), cur=curcumin monoanion (3 and 4) have been designed, synthesized and fully characterized. The X-ray crystal structures of 1 and 2 indicated that the CoN4 O2 core has a distorted octahedral geometry. The photoactivity of these complexes was tuned by varying the π conjugation in the ligands. Curcumin complexes 3 and 4 had an intense absorption band near 435 nm, which made them useful as visible-light photodynamic therapy agents; they also showed fluorescence with λem ≈565 nm. This fluorescence was useful for studying their intracellular uptake and localization in MCF-7 breast cancer cells. The acetylacetonate complexes (1 and 2) were used as control complexes to understand the role of curcumin. The white-light-triggered anticancer profiles of the cytosol targeting complexes 3 and 4 were investigated in detail. These non-dark toxic complexes displayed significant apoptotic photo-cytotoxicity (under visible light) against MCF-7 cells through ROS generation. The control complexes 1 and 2 did not induce significant cell death in the light or dark. Interestingly, 1-4 produced a remarkable antibacterial response upon light exposure. Overall, the reported results here can increase the boundary of the CoII -based anticancer and antibacterial drug development.

Effect of Capsaicin Stress on Aroma-Producing Properties of Lactobacillus plantarum CL-01 Based on E-Nose and GC-IMS.

Capsaicin stress, along with salt stress, could be considered the main stressors for lactic acid bacteria in traditional fermented pepper products. Until now, insufficient attention has been paid to salt stress, while the effect of capsaicin on the aroma-producing properties of Lactobacillus plantarum (L. plantarum) is unclear. The present study attempted to illustrate the effect of capsaicin stress on the aroma-producing properties of L. plantarum CL-01 isolated from traditionally fermented peppers based on E-nose and GC-IMS. The results showed that E-nose could clearly distinguish the overall flavor differences of L. plantarum CL-01 under capsaicin stress. A total of 48 volatile compounds (VOCs) were characterized by means of GC-IMS, and the main VOCs belonged to acids and alcohols. Capsaicin stress significantly promoted L. plantarum CL-01 to produce alpha-pinene, ethyl crotonate, isobutyric acid, trans-2-pentenal, 2-methyl-1-butanol, 3-methyl-3-buten-1-ol, 1-penten-3-one, 2-pentanone, 3-methyl-1-butanol-D, and 2-heptanone (p < 0.05). In addition, under capsaicin stress, the contents of 1-penten-3-one, 3-methyl-3-buten-1-ol, 5-methylfurfuryl alcohol, isobutanol, 2-furanmethanethiol, 2,2,4,6,6-pentamethylheptane, 1-propanethiol, diethyl malonate, acetic acid, beta-myrcene, 2-pentanone, ethyl acetate, trans-2-pentenal, 2-methylbutyl acetate, and 2-heptanone produced by L. plantarum CL-01 were significantly increased along with the fermentation time (p < 0.05). Furthermore, some significant correlations were observed between the response values of specific E-nose sensors and effective VOCs.

PM2.5-mediated photochemical reaction of typical toluene in real air matrix with identification of products by isotopic tracing and FT-ICR MS.

The sight into photoconversion of toluene, a ubiquitous typical pollutant, attentively by the involvement of PM2.5 in the real air environment is crucial for controlling haze pollution. Compared with the large-size PM2.5 on normal day (PM2.5-ND), the PM2.5 on haze day (PM2.5-HD) formed of small particle agglomerates featured greater oxidation capability, evidenced by the valence distribution of sulfur species. Notably, PM2.5-HD had abundant O2-• and •OH and participated in the photochemical reaction of toluene, giving it a greater toluene conversion with a first-order kinetic rate constant of 0.4 d-1 on haze day than on normal day (0.2 d-1). During the toluene photoconversion, isotopic labelling traced small molecules including benzene and newfound pentane, ethylbenzene, 1,3,8-p-menthatriene and 4-methyl-1-pentanone benzene that could be formed by methyl breakage, ring opening, fragmentation reforming and addition reaction of toluene. Given ADMET properties, 1,3,8-p-menthatriene was assigned high priority since it had poor metabolism, low excretion and severe toxicity, while benzene and 4-methyl-1-pentanone benzene should also be noticeable. FT-ICR MS results indicated that toluene could create multiple macromolecular products that are more sensitive to SOA generation in haze air matrix with broader carbon number and O/C, more oxygenated substitution with CHO/CHON occupying by 81.4%, lower DBEaverage at 4.66 and higher OSC‾ at -1.60 than normal air matrix. Accordingly, a photochemical reaction mechanism for toluene in real air atmosphere was proposed. The stronger oxidation property of PM2.5 not only facilitated toluene to generate small molecules but also boosted the conversion of intermediates to oxygenated macromolecular products, contributing to the formation of SOA.

Effects of a redox-active diketone on the photochemical transformation of roxarsone: Mechanisms and environmental implications.

Organoarsenical antibiotics pose a severe threat to the environment and human health. In aquatic environment, dissolved organic matter (DOM)-mediated photochemical transformation is one of the main processes in the fate of organoarsenics. Dicarbonyl is a typical redox-active moiety in DOM. However, the knowledge on the photoconversion of organoarsenics by DOM, especially the contributions of dicarbonyl moieties is still limited. Here, we systematically investigated the photochemical transformation of three organoarsenics with the simplest ß-diketone, acetylacetone (AcAc), as a model dicarbonyl moiety of DOM. The presence of AcAc significantly enhanced the photochemical conversion of roxarsone (ROX), whereas only minor effects were observed for 3-amino-4-hydroxyphenylarsonic acid (HAPA) and arsanilic acid (ASA), because the latter two (with an amino (-NH2) group) are more photoactive than ROX (with a nitro (-NO2) group). The results demonstrate that AcAc was a potent photo-activator and the reduction of -NO2 to -NH2 might be a rate-limiting step in the phototransformation of ROX. At a 1:1 M ratio of AcAc to ROX, the photochemical transformation rate of ROX was increased by 7 folds. In O2-rich environment, singlet oxygen, peroxide radicals, and ·OH were the main reactive species that led to the breakage of the C-As bond in ROX and the oxidation of the released arsono group to arsenate, whereas the triplet-excited state of AcAc (3AcAc*) and carbon-centered radicals from the photolysis of AcAc dominated in the reductive transformation of ROX. In anoxic environment, 3-amino-4-hydroxyphenylarsonic acid was one of the main reductive transformation intermediates of ROX, whose photolysis rate was about 35 times that of ROX. The knowledge obtained here is of great significance to better understand the fate of organoarsenics in natural environment.

Impacts of risk assessment data, assumptions, and methods: Considering the evidence for diacetyl and 2,3-pentanedione.

The articles published as part of the Frontiers in Public Health research topic, "Investigating exposures and respiratory health in coffee workers" present research findings that better characterize exposures to diacetyl and 2,3-pentanedione and inform our understanding of the health risks posed by these exposures. Although various research groups and organizations have conducted risk assessments to derive occupational exposure limits (OELs) for diacetyl, differences in the data used and assumptions made in these efforts have resulted in a wide range of recommended OELs designed to protect human health. The primary drivers of these differences include the decision to use data from human or animal studies in conducting a quantitative risk assessment, and the application of uncertainty factors (UF) to derive an OEL. This Perspectives paper will discuss the practical implications of these decisions, and present additional commentary on the potential role that the recent investigation of human exposures to relatively low concentrations of α-diketones, specifically diacetyl and 2,3-pentanedione, may play in supporting qualitative or quantitative human health risk assessments.

Decrements in lung function and respiratory abnormalities associated with exposure to diacetyl and 2,3-pentanedione in coffee production workers.

Coffee production workers are exposed to complex mixtures of gases, dust, and vapors, including the known respiratory toxins, diacetyl, and 2,3-pentanedione, which occur naturally during coffee roasting and are also present in flavorings used to flavor coffee. This study evaluated the associations of these two α-diketones with lung function measures in coffee production workers. Workers completed questionnaires, and their lung function was assessed by spirometry and impulse oscillometry (IOS). Personal exposures to diacetyl, 2,3-pentanedione, and their sum (SumDA+PD) were assigned to participants, and metrics of the highest 95th percentile (P95), cumulative, and average exposure were calculated. Linear and logistic regression models for continuous and binary/polytomous outcomes, respectively, were used to explore exposure-response relationships adjusting for age, body mass index, tenure, height, sex, smoking status, race, or allergic status. Decrements in percent predicted forced expiratory volume in 1 second (ppFEV1) and forced vital capacity (ppFVC) were associated with the highest-P95 exposures to 2,3-pentanedione and SumDA+PD. Among flavoring workers, larger decrements in ppFEV1 and ppFVC were associated with highest-P95 exposures to diacetyl, 2,3-pentanedione, and SumDA+PD. Abnormal FEV1, FVC, and restrictive spirometric patterns were associated with the highest-P95, cumulative, and average exposures for all α-diketone metrics; some of these associations were also present among flavoring and non-flavoring workers. The combined category of small and peripheral airways plus small and large airways abnormalities on IOS had elevated odds for highest-P95 exposure to α-diketones. These results may be affected by the small sample size, few cases of abnormal spirometry, and the healthy worker effect. Associations between lung function abnormalities and exposure to α-diketones suggest it may be prudent to consider exposure controls in both flavoring and non-flavoring settings.

Retrospective identification of new psychoactive substances in patient samples submitted for clinical drug analysis.

New psychoactive substances (NPS) are life threatening through unpredictable toxicity and limited analytical options for clinicians. We present the retrospective identification of NPS in raw data from a liquid chromatography-high resolution mass spectrometry (LC-HRMS)-based multidrug panel analysis on 14 367 clinical oral fluid samples requested during 2019 mainly by psychiatric and addiction care clinics. Retrospectively analysed NPS included 48 notified originally in 2019 by the European Union Early Warning System (EU EWS) and 28 frequently reported in Sweden. Of 88 included NPS, 34 (mitragynine, flualprazolam, 3F/4F-α-P(i)HP, etizolam, 4F-MDMB-BINACA, cyproheptadine, 5F-MDMB-PICA, isotonitazene, isohexedrone, MDPEP, N-ethylpentedrone, tianeptine, flubromazolam, 4'-methylhexedrone, α-P(i)HP, eutylone, mephedrone, N-ethylhexedrone, 5F-MDMB-PINACA, ADB-BUTINACA, 3-methoxy PCP, 4F-furanylfentanyl, 4F-isobuturylfentanyl, acrylfentanyl, furanylfentanyl, clonazolam, norfludiazepam, 3F-phenmetrazine, 3-MMC, 4-methylpentedrone, BMDP, ethylphenidate, methylone and α-PVP) were identified as 219 findings in 84 patients. Eight NPS notified in 2019 were identified, five before EWS release. NPS occurred in 1.20% of all samples and 1.53% of samples containing traditional drugs, and in 1.87% of all patients and 2.88% of patients using traditional drugs. NPS use was more common in men and polydrug users. Legal (not scheduled) NPS were more used than comparable illegal ones. Retrospective identification could be useful when prioritizing NPS for clinical routine analysis and when studying NPS epidemiology.

Ethyl Vinyl Ketone Activates K+ Efflux to Regulate Stomatal Closure by MRP4-Dependent eATP Accumulation Working Upstream of H2O2 Burst in Arabidopsis.

Plants regulate stomatal mobility to limit water loss and improve pathogen resistance. Ethyl vinyl ketone (evk) is referred to as a reactive electrophilic substance (RES). In this paper, we found that evk can mediate stomatal closure and that evk-induced stomatal closure by increasing guard cell K+ efflux. To investigate the role of eATP, and H2O2 in evk-regulated K+ efflux, we used Arabidopsis wild-type (WT), mutant lines of mrp4, mrp5, dorn1.3 and rbohd/f. Non-invasive micro-test technology (NMT) data showed that evk-induced K+ efflux was diminished in mrp4, rbohd/f, and dorn1.3 mutant, which means eATP and H2O2 work upstream of evk-induced K+ efflux. According to the eATP content assay, evk stimulated eATP production mainly by MRP4. In mrp4 and mrp5 mutant groups and the ABC transporter inhibitor glibenclamide (Gli)-pretreated group, evk-regulated stomatal closure and eATP buildup were diminished, especially in the mrp4 group. According to qRT-PCR and eATP concentration results, evk regulates both relative gene expressions of MRP4/5 and eATP concentration in rbohd/f and WT group. According to the confocal data, evk-induced H2O2 production was lower in mrp4, mrp5 mutants, which implied that eATP works upstream of H2O2. Moreover, NADPH-dependent H2O2 burst is regulated by DORN1. A yeast two-hybrid assay, firefly luciferase complementation imaging assay, bimolecular fluorescence complementation assay, and pulldown assay showed that the interaction between DORN1 and RBOHF can be realized, which means DORN1 may control H2O2 burst by regulating RBOHF through interaction. This study reveals that evk-induced stomatal closure requires MRP4-dependent eATP accumulation and subsequent H2O2 accumulation to regulate K+ efflux.

Functional Studies and Revision of the NFAT-133/TM-123 Biosynthetic Pathway in Streptomyces pactum.

The biosynthetic gene cluster of NFAT-133, an inhibitor of the nuclear factor of activated T cells, was recently identified in Streptomyces pactum ATCC 27456. This cluster is conspicuous by its highly disordered noncollinear type I modular polyketide synthase (PKS) genes that encode PKSs with one module more than those expected for the heptaketide NFAT-133 biosynthesis. Thus, the major metabolite NFAT-133 was proposed to derive from an octaketide analogue, TM-123. Here, we report that further bioinformatic analysis and gene inactivation studies suggest that NFAT-133 is not derived from TM-123 but rather a product of programmed KS7 extension skipping of a nascent heptaketide from the PKS assembly line that produces TM-123. Furthermore, identification of NFAT-133/TM-123 analogues from mutants of the ATCC 27456 strain suggests that NftN (a putative dehydrogenase), NftE (a cytochrome P450), and NftG (a putative hydrolase/decarboxylase) function "in trans" during the polyketide chain assembly processes.

Case Study: Efficacy of Engineering Controls in Mitigating Diacetyl and 2,3-Pentanedione Emissions During Coffee Grinding.

Exposure to elevated levels of diacetyl in flavoring and microwave popcorn production has been associated with respiratory impairment among workers including from a severe lung disease known as obliterative bronchiolitis. Laboratory studies demonstrate damage to the respiratory tract in rodents exposed to either diacetyl or the related alpha-diketone 2,3-pentanedione. Respiratory tract damage includes the development of obliterative bronchiolitis-like changes in the lungs of rats repeatedly inhaling either diacetyl or 2,3-pentanedione. In one flavored coffee processing facility, current workers who spent time in higher diacetyl and 2,3-pentanedione areas had lower lung function values, while five former flavoring room workers were diagnosed with obliterative bronchiolitis. In that and other coffee roasting and packaging facilities, grinding roasted coffee beans has been identified as contributing to elevated levels of diacetyl and 2,3-pentanedione. To reduce worker exposures, employers can take various actions to control exposures according to the hierarchy of controls. Because elimination or substitution is not applicable to coffee production facilities not using flavorings, use of engineering controls to control exposures at their source is especially important. This work demonstrates the use of temporary ventilated enclosures around grinding equipment in a single coffee roasting and packaging facility to mitigate diacetyl and 2,3-pentanedione emissions from grinding equipment to the main production space. Concentrations of diacetyl and 2,3-pentanedione were measured in various locations throughout the main production space as well as inside and outside of ventilated enclosures to evaluate the effect of the enclosures on exposures. Diacetyl and 2,3-pentanedione concentrations outside one grinder enclosure decreased by 95 and 92%, respectively, despite ground coffee production increasing by 12%, after the enclosure was installed. Outside a second enclosure, diacetyl and 2,3-pentanedione concentrations both decreased 84%, greater than the 33% decrease in ground coffee production after installation. Temporary ventilated enclosures used as engineering control measures in this study effectively reduced emissions of diacetyl and 2,3-pentanedione at the source in this facility. These findings motivated management to explore options with a grinding equipment manufacturer to permanently ventilate their grinders to reduce emissions of diacetyl and 2,3-pentanedione.

Acetylacetone Interferes with Carbon and Nitrogen Metabolism of Microcystis aeruginosa by Cutting Off the Electron Flow to Ferredoxin.

The regulation of photosynthetic machinery with a nonoxidative approach is a powerful but challenging strategy for the selective inhibition of bloom-forming cyanobacteria. Acetylacetone (AA) was recently found to be a target-selective cyanocide for Microcystis aeruginosa, but the cause and effect in the studied system are still unclear. By recording of the chemical fingerprints of the cells at two treatment intervals (12 and 72 h with 0.1 mM AA) with omics assays, the molecular mechanism of AA in inactivating Microcystis aeruginosa was elucidated. The results clearly reveal the effect of AA on ferredoxin and the consequent effects on the physiological and biochemical processes of Microcystis aeruginosa. In addition to its role as an electron acceptor of photosystem I, ferredoxin plays pivotal roles in the assimilation of nitrogen in cyanobacterial cells. The effect of AA on ferredoxin and on nonheme iron of photosystem II first cut off the photosynthetic electron transfer flow and then interrupted the synthesis of adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide phosphate (NADPH), which ultimately might affect carbon fixation and nitrogen assimilation metabolisms. The results here provide missing pieces in the current knowledge on the selective inhibition of cyanobacteria, which should shed light on the better control of harmful blooms.