Design, synthesis and anti-oomycete activity of 2-acyloxyhinokitiol derivatives.

In order to explore novel natural product-based anti-oomycete agent, ten 2-acyloxyhinokitiol derivatives (5a-j) were designed and synthesised, and structurally confirmed by 1H NMR,13C NMR, HRMS, and melting point. The stereochemical configuration of compound 5f was unambiguously confirmed by single-crystal X-ray diffraction. Furthermore, we evaluated the target compounds 5a-j as anti-oomycete activity against a serious agricultural disease of Phytophthora capsici. Among the ten hinokitiol ester derivatives tested, four compounds 5d, 5g, 5h and 5j had anti-oomycete activity higher than the positive control zoxamide (EC50 = 23.59 mg/L), and the EC50 values of 18.90, 20.62, 13.61 and 21.29 mg/L, respectively. Especially compound 5h exhibited the best anti-oomycete activity against P. capsici with EC50 value of 13.61 mg/L. Overall, the anti-oomycete activities of 2-acyloxyhinokitiol derivatives is higher than that of 2-sulfonyloxyhinokitiol derivatives. The results laid a good foundation for the subsequent synthesis of hinokitiol ester derivatives with significant anti-oomycete activity.

Cell-fate conversion of intestinal cells in adult Drosophila midgut by depleting a single transcription factor.

The manipulation of cell identity by reprograming holds immense potential in regenerative medicine, but is often limited by the inefficient acquisition of fully functional cells. This problem can potentially be resolved by better understanding the reprogramming process using in vivo genetic models, which are currently scarce. Here we report that both enterocytes (ECs) and enteroendocrine cells (EEs) in adult Drosophila midgut show a surprising degree of cell plasticity. Depleting the transcription factor Tramtrack in the differentiated ECs can initiate Prospero-mediated cell transdifferentiation, leading to EE-like cells. On the other hand, depletion of Prospero in the differentiated EEs can lead to the loss of EE-specific transcription programs and the gain of intestinal progenitor cell identity, allowing cell cycle re-entry or differentiation into ECs. We find that intestinal progenitor cells, ECs, and EEs have a similar chromatin accessibility profile, supporting the concept that cell plasticity is enabled by pre-existing chromatin accessibility with switchable transcription programs. Further genetic analysis with this system reveals that the NuRD chromatin remodeling complex, cell lineage confliction, and age act as barriers to EC-to-EE transdifferentiation. The establishment of this genetically tractable in vivo model should facilitate mechanistic investigation of cell plasticity at the molecular and genetic level.

Combinatorial Synthesis of Indole Derivatives as Anti-oomycetes Agents.

BACKGROUND: Developing high-efficiency and low-risk small-molecule green fungicide is the key to effective control of the plant pathogenic oomycetes. Indole is an important raw material for drug synthesis. Due to its unique structural skeleton, indole, and its derivatives have exhibited a wide range of biological activities. However, a study on the synthesis of novel indole derivatives as fungicidal agents against Phytophthora capsici has not yet been reported. METHODS: The important intermediates 2a-c and 3a-c were synthesized in high yields by Vilsmeier- Haack and Knoevenagel reactions with indole as the lead compound. Furthermore, different substituted benzenesulfonyl groups were introduced into the NH position of the indole ring, and twelve indole derivatives (I-a-l) were prepared. Their structures were well characterized by 1H NMR, HRMS, and melting point. RESULTS: The results showed that 2-[(N-(4-nitrobenzenesulfonyl)-indole-3)-methylene]-diethyl malonate (I-d) and 2-[(N-(4-nitrobenzenesulfonyl)-5-cyanoindole-3)-methylene]-diethyl malonate (I-l) showed more anti-oomycete activity against P. capsici than the commercialized fungicide zoxamide, with corresponding EC50 values of 26.53, 23.48 and 28.16 mg/L, respectively, and the protective effect of the compounds against P. capsici in vivo further confirmed the above results. CONCLUSION: The preliminary structure-activity relationship showed that the formyl group modification at the C-3 position of the indole ring was acceptable, and the different anti-oomycete activities of R1 and R2 were significantly different, with R1 being 5-CN > H > 6-Me, and R2 being 4-NO2 > 3-NO2, H > 4-Me.

Synthesis of novel 18ß-glycyrrhetinic acid sulfonate derivatives displaying significant anti-oomycete activity against Phytophthora capsici.

Using 18ß-glycyrrhetinic acid (GA) as the lead compound, fourteen GA sulphonate derivatives (3a-n) were prepared by modifying its C-3 OH group, and their structures were well confirmed by 1H NMR, 13C NMR, HRMS and melting points. Moreover, we screened the anti-oomycete activity of these compounds against Phytophthora capsici by using the mycelial growth rate method. Among the fourteen GA sulphonate derivatives evaluated, four compounds 3f, 3j, 3k and 3l exhibited more potent anti-oomycete activity than that of the positive control zoxamide (EC50 = 25.17 mg/L), and had the median effective concentration (EC50) values of 23.04, 16.16, 22.55, and 13.93 mg/L, respectively. Especially compound 3l showed the best anti-oomycete activity against P. capsici with EC50 value of 13.93 mg/L. Overall, the introduction of sulfonyloxy groups at the C-3 position of GA has a significant impact on its anti-oomycete activity, and the corresponding derivative activity varies significantly with different substituents R.

Terahertz Metasurfaces Exploiting the Phase Transition of Vanadium Dioxide.

Artificially designed modulators that enable a wealth of freedom in manipulating the terahertz (THz) waves at will are an essential component in THz sources and their widespread applications. Dynamically controlled metasurfaces, being multifunctional, ultrafast, integrable, broadband, high contrasting, and scalable on the operating wavelength, are critical in developing state-of-the-art THz modulators. Recently, external stimuli-triggered THz metasurfaces integrated with functional media have been extensively explored. The vanadium dioxide (VO2)-based hybrid metasurfaces, as a unique path toward active meta-devices, feature an insulator-metal phase transition under the excitation of heat, electricity, and light, etc. During the phase transition, the optical and electrical properties of the VO2 film undergo a massive modification with either a boosted or dropped conductivity by more than four orders of magnitude. Being benefited from the phase transition effect, the electromagnetic response of the VO2-based metasufaces can be actively controlled by applying external excitation. In this review, we present recent advances in dynamically controlled THz metasurfaces exploiting the VO2 phase transition categorized according to the external stimuli. THz time-domain spectroscopy is introduced as an indispensable platform in the studies of functional VO2 films. In each type of external excitation, four design strategies are employed to realize external stimuli-triggered VO2-based THz metasurfaces, including switching the transreflective operation mode, controlling the dielectric environment of metallic microstructures, tailoring the equivalent resonant microstructures, and modifying the electromagnetic properties of the VO2 unit cells. The microstructures' design and electromagnetic responses of the resulting active metasurfaces have been systematically demonstrated, with a particular focus on the critical role of the VO2 films in the dynamic modulation processes.

Volatile fatty acids changed the microbial community during feammox in coastal saline-alkaline paddy soil.

In order to indicate the effect of volatile fatty acids (VFAs) on the characteristics of feammox and dissimilatory iron reducing bacteria (DIRB) in paddy soils, different VFAs were selected with paddy soils for anaerobic cultivation. Five treatments were set up, respectively, only adding N and both adding N and C (formate + NH4+ (Fo-N), acetate + NH4+ (Ac-N), propionate + NH4+ (Pr-N), and butyrate + NH4+ (Bu-N)) treatments. The concentration of Fe(II), Fe(III), NH4+, and VFAs was assessed within 45 d, and the bacterial community was determined after cultivation. The oxidation rates of NH4+ were the highest in N treatment, while it was the lowest in Fo-N treatment. Under the four C treatments, the consumption of NH4+ and Fe(III) was the fastest in Pr-N treatment, which was consumed by 31.2% and 76.3%, respectively. Different VFAs selected for distinct DIRB. Compared with N treatment, Ac-N and Bu-N treatment increased the relative abundance of DIRB, such as Geobacter and Clostridia, which increased the consumption of VFAs during incubation. Overall, VFAs, especially formate, could promote Fe(III) reduction and compete with the feammox process for the electron acceptors to decrease the feammox reaction, and prohibited soil NH4+ loss. Therefore, VFAs, which was released from organic fertilizer, could reduce NH4+ loss in feammox process of saline-alkaline paddy soils.

Synthesis of paeonol ester derivatives and their insecticidal, nematicidal, and anti-oomycete activities.

BACKGROUND: Paeonol is extracted and isolated as a rich and sustainable natural bioresource from the root bark of Paeonia suffruticosa, the derivatives of which exhibit numerous biological activities. It is well known that ester compounds play a very important role in pest control, such as organophosphorus, carbamate and pyrethroid pesticides. RESULTS: To discover biorational natural product-based pesticides, three series of (60) paeonol ester derivatives (7a-t, 8g,p, 9g,p, 10g-j,n-u, 11g,u, 12g,u, 13a-p, 14b,c, and 15b,c) were prepared by structural modification of paeonol, and their structures were well characterized by proton nuclear magnetic resonance (1 H-NMR), carbon-13 nuclear magnetic resonance (13 C-NMR), high-resolution mass spectrometry (HRMS), and melting point. Furthermore, we assessed the compounds as insecticidal, nematicidal, and anti-oomycete agents against three serious agricultural pests, Mythimna separata, Heterodera glycines, and Phytophthora capsici. Among all tested compounds: (i) compound 8p showed more significant insecticidal activity than toosendanin, and the final mortality rates of 8p and toosendanin against M. separata (1 mg mL-1 ) were 70.4%, and 51.9%, respectively; (ii) compound 7a exhibited more promising nematicidal activity than paeonol, and the median lethal concentration (LC50 ) values of 7a and 1 against H. glycines were 15.47 and 50.80 mg L-1 , respectively; (iii) compounds 7n and 13m displayed more significant anti-oomycete activity compared to zoxamide against Phytophthora capsici, and the median effective concentration (EC50 ) values of 7n, 13m, and zoxamide were 23.72, 24.51, and 26.87 mg L-1 , respectively; and the protective effect of the compounds against Phytophthora capsici in vivo further confirmed the effectiveness of the agents. CONCLUSION: This study suggested that the introduction of a nitro at the C5 or C3 position of paeonol could improve its bioactivity against M. separata, H. glycines, and Phytophthora capsici. © 2022 Society of Chemical Industry.

Synthesis and Anti-Oomycete Preliminary Mechanism of Sulfonate Derivatives of Ethyl Maltol.

To discover novel molecules with unique mechanism against plant pathogenic oomycetes, sixteen new sulfonate derivatives of ethyl maltol (3a-p) were synthesized by structural modification of 2-ethyl-3-hydroxy-4H-pyran-4-one, and their anti-oomycete activity against a serious agricultural disease, Phytophthora capsici Leonian was determined in this study. Among all tested compounds, derivatives 3e, 3m and 3p exhibited the most potent anti-oomycete activity against P. capsici with EC50 values of 19.40, 21.04 and 31.10 mg/L, respectively; especially 3e and 3m showed the best promising and pronounced anti-oomycete activity than zoxamide (EC50 =26.87 mg/L). The results further proved that 4-tert-butylphenylsulfonyl group, 3-nitro-4-chlorophenylsulfonyl group and 8-quinolinesulfonyl group introduced at the hydroxy position of ethyl maltol or maltol were necessary for obtaining the most potent compounds. Further mechanism studies of P. capsici treated with 3e demonstrated that this compound can affect the growth of mycelia by disrupting the integrity of the membrane, and the higher the concentration of the compound is, the greater the degree of membrane integrity damage. These important results will pave the way for further modification of ethyl maltol to develop potential new fungicides.

Synthesis and Anti-Oomycete Activity of Sulfonate Derivatives of Fenjuntong.

In order to discover highly active fungicides, sixteen novel sulfonate derivatives of Fenjuntong were synthesized by structural modification of 2'-hydroxybutyrophenone, and their anti-oomycete activity against Phytophthora capsici Leonian was determined in this study. Among all tested compounds, compound 3b displayed more significant anti-oomycete activity than the precursor Fenjuntong against P. capsici, and the EC50 values of 3b and Fenjuntong were 84.50 and 517.25 mg/L, respectively. By comparing the anti-oomycete activity of compounds 3a-p, I-a-p, and II-a-p, the following conclusions were drawn: (1) Hydroxy group is well tolerated, and sulfonylation of hydroxy group enhances its anti-oomycete activity. (2) The proper length of the ketone carbonyl chain is very important for their anti-oomycete activity. (3) The presence of a site methoxy group in the structural skeleton is closely related to the anti-oomycete activity. These important results will pave the way for further modification of Fenjuntong to develop potential new fungicides.

Label-Free Imaging of Single Nanoparticles Using Total Internal Reflection-Based Leakage Radiation Microscopy.

Label-free, fast, and single nanoparticle detection is demanded for the in situ monitoring of nano-pollutants in the environment, which have potential toxic effects on human health. We present the label-free imaging of single nanoparticles by using total internal reflection (TIR)-based leakage radiation microscopy. We illustrate the imaging of both single polystyrene (PS) and Au nanospheres with diameters as low as 100 and 30 nm, respectively. As both far-field imaging and simulated near-field electric field intensity distribution at the interface showed the same characteristics, i.e., the localized enhancement and interference of TIR evanescent waves, we confirmed the leakage radiation, transforming the near-field distribution to far-field for fast imaging. The localized enhancement of single PS and Au nanospheres were compared. We also illustrate the TIR-based leakage radiation imaging of single polystyrene nanospheres with different incident polarizations. The TIR-based leakage radiation microscopy method is a competitive alternative for the fast, in situ, label-free imaging of nano-pollutants.

Detecting the morphology of single graphene sheets by dual channel sampling plasmonic imaging.

Due to their excellent physical and chemical properties, graphene sheets are widely used in industry, which makes detection important to guarantee their performance. Atomic force microscopy, scanning electron microscopy, and Raman spectroscopy are the most common detection methods, which is either time-consuming or easily destructive. In this work, we presented a fast and nondestructive method to detect single graphene sheets by using plasmonic imaging. Dual channel sampling plasmonic imaging combining the image processing algorithm is used to improve the deterioration from propagation length of surface plasmon polaritons and reconstruct the complete morphology of single graphene sheets. The fast and nondestructive detection method paves the way to applications of graphene, and can be extended to the detections of two-dimensional materials, single biological molecule, viruses, and nanomaterials.

Detecting a single nanoparticle by imaging the localized enhancement and interference of surface plasmon polaritons: erratum.

In this erratum, the function ${\lambda _{{\rm SPP}}}$λSPP in the third page of Opt. Lett.44, 5707 (2019)OPLEDP0146-959210.1364/OL.44.005707 has been corrected.

Detecting a single nanoparticle by imaging the localized enhancement and interference of surface plasmon polaritons.

Label-free single-nanoparticle detection is crucial for the fast detection of nanoparticles and viruses in environmental monitoring and biological sciences. In this Letter, benefiting from the leakage radiation that transforms the near-field surface plasmon polariton (SPP) distribution along the interface to the far field, we demonstrated the plasmonic imaging of single polystyrene nanoparticles with a particle size down to 39 nm. The imaging is composed of the localized enhancement and interference of SPPs. The localized enhancement is the result of the accumulation of charges around the nanoparticle, and it is connected to the size and refractive index of nanoparticles. The interference is induced by the coupling between the incident SPPs and the scattered SPPs, verified by extracting the interference fringe periodicity to be half of the SPP wavelength. Our study provides an in-depth physical understanding of plasmonic imaging of single nanoparticles, which paves the way for a fast identification of nanomaterials.

Embryonic stem-like cells from rabbit blastocysts cultured with melatonin could differentiate into three germ layers in vitro and in vivo.

The rabbit is considered an important model animal from which to obtain embryonic stem cells because of the utility of this animal in physiology and reproductive research. Here, we derived rabbit ES-like (rES-like) cells from blastocysts of superovulated Japanese white rabbits using culture medium containing 10-7 M melatonin, 10 ng/mL basic fibroblast growth factor, and 1,000 IU/mL human leukemia inhibitory factor. This concentration of melatonin had the most significant positive effects on the proliferation inner cell mass-derived cells (improving rates from 19.97% to 34.57%) and the longevity of passaging rES-like cells. Melatonin also enhanced the expression of pluripotent genes-including alkaline phosphatase, Pou5f1, Sox2, Klf4, c-Myc, Nanog, Line28a, and surface marker proteins-in fifth-passage rES-like cells. In vitro, these rES-like cells could spontaneously differentiate into some somatic cells, such as beating cardiomyocytes; formed embryoid bodies; expressed markers of the three germ layers after differentiation; and formed teratomas after injection into non-obese diabetic-severe combined immune deficient (NOD-SCID) mice. Thus, melatonin helped coax ES-like cells from rabbit blastocysts, which raises intriguing questions about the relationship between pluripotency and proliferation in rabbit embryonic stem cells. Mol. Reprod. Dev. 83: 1003-1014, 2016 © 2016 Wiley Periodicals, Inc.