Regioselectivity Switch of α-Amino Acid-Derived Esters and MBH Carbonates for the Synthesis of Allyl-Substituted Azlactones.

Allylic azlactones are greatly significant in terms of potential bioactivities and synthetic applications. Owing to the burgeoning interest of the pharmaceutical industry in α-amino acid derivatives, discovering strategies for the synthesis of allylic azlactones is important. Herein, we establish a transition-metal-free regioselectivity switch of α-amino acid-derived esters and MBH carbonates, which exhibits broad reaction scope and good reaction yields. Control reactions indicate that both base and solvent are important for regioselectivity.

Chemical Constituents and Bioactivities of the Plant-Derived Fungus Aspergillus fumigatus.

A new bergamotane sesquiterpenoid, named xylariterpenoid H (1), along with fourteen known compounds (2-15), were isolated from the crude extract of Aspergillus fumigatus, an endophytic fungus isolated from Delphinium grandiflorum L. Their structures were elucidated mainly by extensive analyses of NMR and MS spectroscopic data. In addition, the screening results of antibacterial and cytotoxic activities of compounds 1-15 showed that compound 4 displayed antibacterial activities against Staphylococcus aureus and MRSA (methicillin-resistant S. aureus) with an MIC value of 3.12 µg/mL.

Rosemary: Unrevealing an old aromatic crop as a new source of promising functional food additive-A review.

Rosemary (Rosmarinus officinalis L.) is one of the most famous spice plants belonging to the Lamiaceae family as a remarkably beautiful horticultural plant and economically agricultural crop. The essential oil of rosemary has been enthusiastically welcome in the whole world for hundreds of years. Now, it is wildly prevailing as a promising functional food additive for human health. More importantly, due to its significant aroma, food, and nutritional value, rosemary also plays an essential role in the food/feed additive and food packaging industries. Modern industrial development and fundamental scientific research have extensively revealed its unique phytochemical constituents with biologically meaningful activities, which closely related to diverse human health functions. In this review, we provide a comprehensively systematic perspective on rosemary by summarizing the structures of various pharmacological and nutritional components, biologically functional activities and their molecular regulatory networks required in food developments, and the recent advances in their applications in the food industry. Finally, the temporary limitations and future research trends regarding the development of rosemary components are also discussed and prospected. Hence, the review covering the fundamental research advances and developing prospects of rosemary is a desirable demand to facilitate their better understanding, and it will also serve as a reference to provide many insights for the future promotion of the research and development of functional foods related to rosemary.

Anti-MRSA Dimeric and Brominated Phenyltetracenoids Produced by Streptomyces morookaense SC1169.

Eleven new phenyltetracenoid polyketides, streptovertimycins U (1) and V (2), 14-bromo-streptovertidione (3), streptovertimycins W-Y (4-6), and streptovertimycins Z1-Z5 (7-11), together with the known congeners fasamycins R (12) and S (13) and accramycins A (14) and B (15), were isolated from the NaBr-supplemented rice-grown cultures of Streptomyces morookaense SC1169. Their structures were elucidated by extensive spectroscopic analysis, single-crystal X-ray diffraction analysis, and theoretical computations of ECD spectra. Compounds 1 and 2 are methylene-bridged dimers of accramycin A, and compounds 3 and 7-11 are brominated fasamycin congeners. Compounds 5 and 8-14 exhibited activity against the drug-resistant bacteria MRSA and VRE (MIC = 0.6-5.0 µg/mL), and the dimer 1 displayed activity against MRSA (MIC = 2.5 µg/mL). Compounds 6-15 showed cytotoxicity against the human carcinoma A549, HeLa, HepG2, and MCF-7 cells in the IC50 range between 1.7 and 9.2 µM.

Koninginins X-Z, Three New Polyketides from Trichoderma koningiopsis SC-5.

Koninginins X-Z (1-3), three novel polyketides, were isolated from the solid fermentation of the endophytic fungus Trichoderma koningiopsis SC-5. Their structures, including the absolute configurations, were comprehensively characterized by a combination of NMR spectroscopic methods, HRESIMS, 13C NMR, DFT GIAO 13C NMR, and electronic circular dichroism calculations as well as single crystal X-ray diffraction. In addition, all the compounds were evaluated for antifungal activity against Candida albicans.

Pyrone and isocoumarin derivatives from the endophytic fungus Cytospora rhizophorae.

Cytospone A (1), a pyrone and isocoumarin hetero-dimer possessing an unprecedented skeleton with a polyoxygen-hetero 6/6/6/6 tetracyclic fused ring system, and three other biosynthetic precursors cytospones B-D (2-4), along with eleven known compounds were purified from Cytospora rhizophorae A761. The deduced structure of cytospone A represents the first family of natural hetero-dimers comprising pyrone and isocoumarin moieties. A plausible biogenetic pathway involving an intriguing Knoevenagel condensation/6π electrocyclization cascade sequence as the key chemical transformation is proposed.

Concise total syntheses of two flavans and structure revision assisted by quantum NMR calculations.

A two-step protecting-group-free protocol for the synthesis of 3'-hydroxy-5,7-dimethoxy-4-O-2'-cycloflavan (1) and concise total synthesis of 4'-hydroxy-5,7-dimethoxy-4-O-2'-cycloflavan (8) enabled by a PTSA triggered bioinspired olefin isomerization/hemiacetalization/dehydration/[3 + 3]-type cycloaddition cascade reaction are reported. The successful synthesis of cycloflavan 8 along with GIAO 13C NMR calculations of flavan-4-ol 9 and cycloflavan 8 indicated the misassignment of the flavonoid isolated previously and realized the revision of its actual structure.

Neocucurbins A-G, novel macrocyclic diterpenes and their derivatives from Neocucurbitaria unguis-hominis FS685.

Three novel phomactin diterpenes neocucurbins A-C (1-3) and their derivatives, neocucurbins D-G (4-7), were isolated from the marine-derived fungus Neocucurbitaria unguis-hominis FS685. Among them, neocucurbins A-C represent the first examples of the phomactin family with an unprecedented skeleton sharing a novel polyoxygen-hetero 5/6/12 or 5/6/13 fused tricyclic ring system; whereas neocucurbins D-G feature a 5/6 fused bicyclic ring system with the opening of the macrocyclic ring, which was found in the phomactin family for the first time. Moreover, spectroscopic data analyses, single-crystal X-ray diffraction experiments, and ECD calculations were conducted to illustrate the absolute configurations of their structures. Furthermore, all seven compounds (1-7) were evaluated for their cytotoxic and antimicrobial activities.

Total syntheses of melodienones by redox isomerization of propargylic alcohols.

A remarkable base-promoted methodology for the rapid construction of the (E)- and (Z)-γ-oxo-α,ß-alkenoic ester skeletons from readily accessible vinyl propargylic alcohols through modified redox isomerization was uncovered. This approach manifested its high simplicity and efficiency with excellent tolerance of functional substituents, which led to the straightforward structural modifications of various natural products and efficient total syntheses of melodienone, homomelodienone, isomelodienone, and homoisomelodienone within 4 linear steps.

Sesquiterpenes and Steroids from an Endophytic Eutypella scoparia.

A chemical investigation on the EtOAc extract of the endophytic fungus Eutypella scoparia SCBG-8 led to the isolation of eight new sesquiterpenes eutyscoparins A-H (1-8), one C-28 steroid eutyscoparene A (9), one triterpenoid eutyscoparene B (10), six known terpenoids, and two known steroids. Their structures including absolute configurations were established on the basis of spectroscopic data analysis, single-crystal X-ray diffraction experiments, and electronic circular dichroism (ECD) calculations. Compound 7 displayed antibacterial activity against S. aureus and MRSA (methicillin-resistant Staphylococcus aureus) with MIC values of 6.3 µg/mL.

Improvement of RTT Fairness Problem in BBR Congestion Control Algorithm by Gamma Correction.

Google proposed the bottleneck bandwidth and round-trip propagation time (BBR), which is a new congestion control algorithm. BBR creates a network path model by measuring the available bottleneck bandwidth and the minimum round-trip time (RTT) to maximize delivery rate and minimize latency. However, some studies have shown that there are serious RTT fairness problems in the BBR algorithm. The flow with longer RTT will consume more bandwidth and the flows with shorter RTT will be severely squeezed or even starved to death. Moreover, these studies pointed out that even small RTT differences will lead to the throughput of BBR flows being unfair. In order to solve the problem of RTT fairness, an improved algorithm BBR-gamma correction (BBR-GC) is proposed. BBR-GC algorithm takes RTT as feedback information, and then uses the gamma correction function to fit the adaptive pacing gain. This approach can make different RTT flows compete for bandwidth more fairly, thus alleviating the RTT fairness issue. The simulation results of Network Simulator 3 (NS3) show that that BBR-GC algorithm cannot only ensure the channel utilization, but also alleviate the RTT fairness problem of BBR flow in different periods. Through the BBR-GC algorithm, RTT fairness is improved by 50% and the retransmission rate is reduced by more than 26%, compared with that of the original BBR in different buffer sizes.

Lithocaldehydes A and B, polyketones from the deep sea-derived fungus Phomopsis lithocarpus FS508.

Lithocaldehydes A (1) and B (2), a pair of novel diastereoisomers possessing an unprecedented 6/6/5/5/6 highly-fused ring system forming an earring-like skeleton, were isolated from the deep sea-derived fungus Phomopsis lithocarpus FS508. The structures of 1 and 2 were fully characterized and established through extensive spectroscopic interpretations and ECD calculations. Moreover, compounds 1 and 2 were shown to be promising antibiotics, exhibiting potent antifungal activities that are comparable to those of the positive control nystatin.

Structural elucidation, total synthesis, and cytotoxic activity of effphenol A.

A highly substituted phenol derivative, effphenol A (1), was isolated from the deep-sea-derived fungus Trichobotrys effuse FS524. Its complete structural assignment was established through a combination of spectroscopic analysis together with single-crystal X-ray diffraction experiments and further unequivocally confirmed by a biomimetic total synthesis. Structurally, effphenol A possesses a poly-substituted 6-5/6/6 tetracyclic ring system, which represents the first case of such a skeleton found in nature. Furthermore, the cytotoxic activity of effphenol A (1) toward four human cancer cell lines was assayed.

Photeroids A and B, unique phenol-sesquiterpene meroterpenoids from the deep-sea-derived fungus Phomopsis tersa.

Photeroids A (1) and B (2), two structurally fascinating meroterpenoids, were isolated from the deep-sea-derived fungus Phomopsis tersa FS441. Their structures were sufficiently established by a comprehensive interpretation of the spectroscopic data, NMR spectra, and ECD calculation. Photeroids A and B represented the first phenolic sesquiterpene meroterpenoids featuring a highly fused 6/6/6/6 tetracyclic ring system derived through a rarely-occurring hetero-Diels-Alder reaction via an orthoquinone methide intermediate. Additionally, they were also evaluated for their cytotoxic activities against four human cancer cells, wherein compounds 1 and 2 exhibited moderate cytotoxic activities.

The First Racemic Total Syntheses of the Antiplasmodials Watsonianones A and B and Corymbone B.

The first biomimetic total syntheses of three biologically meaningful acylphloroglucinols, watsonianones A and B and corymbone B, with potent antiplasmodial activity, were performed. Their total syntheses were carried out through a diversity-oriented synthetic strategy from congener 2,2,4,4-tetramethyl-6-(3-methylbutylidene)cyclohexane-1,3,5-trione with high step efficiency. The spontaneous enolization/air oxidation of the precursor 2,2,4,4-tetramethyl-6-(3-methylbutylidene)cyclohexane-1,3,5-trione through a singlet O2-induced Diels-Alder reaction pathway to assemble the key biosynthetic peroxide intermediate is also discussed.

Antibacterial sesquiterpenes from the stems and roots of Thuja sutchuenensis.

Eight new sesquiterpenes with diverse skeletons involving four cuparenes, denominated thujasutchins F-I (1-4), one eudesmane and one cedrol, named thujasutchin J (5) and thujasutchin K (6), as well as two thujopsenes thujasutchins L-M (7-8) together with three known congener compounds (9-11) were isolated from EtOAc soluble fraction of ethanolic extract of the stems and roots of Thuja sutchuenensis. Their structures including absolute configurations were unambiguously established by extensive interpretation of the NMR and mass spectroscopic data, X-ray diffractions, and ECD measurements powered by molecular calculations. The biological assays disclosed that 5 and 9 displayed potent inhibitory effect against Staphylococcus. aureus (CMCC 26003), methicillin-resistant Staphylococcus aureus (JCSC 4744), Bacillus cereus (ATCC 10876), and Staphylococcus epidermidis (ATCC 12228) with MICs ranging from 6.25 to 25 µg/mL.

Highly Substituted Phenol Derivatives with Nitric Oxide Inhibitory Activities from the Deep-Sea-Derived Fungus Trichobotrys effuse FS524.

Chemical investigation on EtOAc extract of the deep-sea-derived fungus Trichobotrys effuse FS524 resulted in the isolation of six new highly substituted phenol derivatives trieffusols A-F (1-6), along with ten known relative analogues (7-16). Their structures with absolute configurations were extensively characterized on the basis of spectroscopic data analyses, single-crystal X-ray diffraction experiments, and electronic circular dichroism (ECD) calculations. Structurally, trieffusols A and B shared an unprecedented ploy-substituted 9-phenyl-hexahydroxanthone skeleton with an intriguing 6-6/6/6 tetracyclic fused ring system, which were often encountered as significant moieties in the pharmaceutical drugs but rarely discovered in natural products. In the screening towards their anti-inflammatory activities of 1-6, trieffusols C and D exhibited moderate inhibitory activities against nitric oxide (NO) production in LPS-induced RAW 264.7 macrophages with IC50 values ranging from 51.9 to 55.9 µM.

Coordination breakdowns in nuclear power plant control rooms: cause identification and behaviour-sequence analysis.

This study aims to identify the causes of coordination breakdowns among control crews and to understand their coordination-behaviour patterns during emergencies in nuclear power plants (NPPs). On the basis of in-depth interviews with 18 control-crew operators, we identified 25 causes of coordination breakdown related to work processes, personnel, and situation and organisation. In addition, we observed 12 control-crew training sessions that dealt with emergencies and conducted lag-sequential analysis. The levels of coordination effectiveness were evaluated using the proportion of coordination breakdowns and the anticipation ratio. We found that higher-performing teams exhibited more non-random coordination behavioural patterns than did lower-performing teams. Coordination-behaviour patterns specific to the higher-performing teams included adaptive workload management (from senior operators) and proactive seeking performance monitoring (from junior operators). The findings of the study enrich our understanding of the critical factors and processes that influence coordination effectiveness of NPP control crews. Practitioner summary: Causes of coordination breakdowns among control crews of NPPs were identified based on in-depth interviews with control-crew operators, and behavioural-pattern analysis of control crews in 12 training sessions were analysed to reveal the patterns that differentiate higher- and lower-performing teams. The findings of the study enrich our understanding of the critical factors and processes that influence the coordination effectiveness of NPP control crews. Abbreviations: NPP: nuclear power plant; RO: reactor operator; TO: turbine operator; CO: coordinator; SRO: senior reactor operator.

Rhizophols A and B, antioxidant and axially chiral benzophenones from the endophytic fungus Cytospora rhizophorae.

Two novel polyketones, rhizophols A-B (1-2), were isolated from the endophytic fungus Cytospora rhizophorae A761. They shared unprecedented poly-substituted benzophenone skeletons featuring an epoxy isopentyl unit and a propionyl moiety. Their structures were evidenced by extensive spectroscopic analyses, X-ray diffraction, and quantum energy calculation. Moreover, compound 1 was proved to be a promising lead compound for novel antioxidant drugs.

Cytosporins A-D, novel benzophenone derivatives from the endophytic fungus Cytospora rhizophorae A761.

Four novel benzophenone derivatives, cytosporins A-D (1-4), hemiterpene-conjugated phenolics with an unprecedented benzo[b][1,5]dioxocane skeleton, were isolated from Cytospora rhizophorae A761. The structures of the new compounds were fully characterized on the basis of extensive spectroscopic analysis. The deduced structure represents the first example of natural meroterpenoids which bear a benzo[b][1,5]dioxocane framework embodying hemiterpene and benzophenone moieties. Moreover, compounds 1-4 were evaluated for in vitro antimicrobial activity.