Design and Synthesis of Novel Xyloketal Derivatives and Their Protective Activities against H2O2-Induced HUVEC Injury

In this work, we designed and synthesized a series of amide derivatives (1–13), benzoxazine derivatives (16–28) and amino derivatives (29–30) from xyloketal B. All 28 new derivatives and seven known compounds (14, 15, 31–35) were evaluated for their protection against H₂O₂-induced HUVEC injury. 23 and 24 exhibited more potential protective activities than other derivatives; and the EC₅₀ values of them and the leading compound 31 (xyloketal B) were 5.10, 3.59 and 15.97 μM, respectively. Meanwhile, a comparative molecular similarity indices analysis (CoMSIA) was constructed to explain the structural activity relationship of these xyloketal derivatives. This 3D QSAR model from CoMSIA suggested that the derived model exhibited good predictive ability in the external test-set validation. Derivative 24 fit well with the COMSIA map, therefore it possessed the highest activity of all compounds. Compounds 23, 24 and 31 (xyloketal B) were further to examine in the JC-1 mitochondrial membrane potential (MMP) assay of HUVECs using flow cytometry (FCM). The result indicated that 23 and 24 significantly inhibited H₂O₂-induced decrease of the cell mitochondrial membrane potential (ΔΨm) at 25 μM. Collectively, the protective effects of xyloketals on H₂O₂-induced endothelial cells may be generated from oxidation action by restraining ROS and reducing the MMP.     

Rheological behavior of magnetic carbon nanotubes and their application as kevlar coating

Carbon nanotube (CNT)/magnetite (Fe₃O₄) nanocomposites were successfully fabricated by nanocoating. When the CNT/Fe₃O₄ nanocomposites were added to a carbonyl (CI) based magnetorheological fluid (MRF), the magnetic rheological properties of the MRF were enhanced. Such enhancement in magnetic rheological properties of the CI-CNT/Fe₃O₄ MRF is considered to be attributable to both the superparamagnetic property of the magnetic layer covering the CNT surface and the high length to diameter ratio of the CNT/Fe₃O₄ nanocomposite. Impact properties for CI-CNT/Fe₃O₄ MRF treated Kevlar fabrics were also tested, and improved impact properties were observed with external magnetic fields compared to CI-MRF treated Kevlar fabrics.     

Localization and Characterization of Ferritin in Demospongiae: A Possible Role on Spiculogenesis

Iron, as inorganic ion or as oxide, is widely used by biological systems in a myriad of biological functions (e.g., enzymatic, gene activation and/or regulation). In particular, marine organisms containing silica structures—diatoms and sponges—grow preferentially in the presence of iron. Using primary sponge cell culture from S. domuncula–primmorphs—as an in vitro model to study the Demospongiae spiculogenesis, we found the presence of agglomerates 50 nm in diameter exclusively inside sponge specialized cells called sclerocytes. A clear phase/material separation is observed between the agglomerates and the initial stages of intracellular spicule formation. STEM-HRTEM-EDX analysis of the agglomerates (30–100 nm) showed that they are composed of pseudohexagonal nanoparticles between 5 and 15 nm in size, displaying lattice parameters corresponding to hematite (Fe₂O₃) and mixed iron oxide phases typically attributed to ferritin. Further analysis, using western blotting, inductively coupled plasma mass spectrometry (ICP-MS), sequence alignment analysis, immunostaining and magnetic resonance imaging (MRI), of mature spicule filaments confirm the presence of ferritin within these organic structures. We suggest that S. domuncula can be classified as a dual biomineralizating organism, i.e., within the same cellular structure two distinct biomineralizing processes can occur as a result of the same cellular/metabolic function, spiculogenesis.     

Affinity Purification of Angiotensin Converting Enzyme Inhibitory Peptides from Wakame (Undaria Pinnatifida) Using Immobilized ACE on Magnetic Metal Organic Frameworks

Angiotensin-I-converting enzyme (ACE) inhibitory peptides derived from marine organism have shown a blood pressure lowering effect with no side effects. A new affinity medium of Fe₃O₄@ZIF-90 immobilized ACE (Fe₃O₄@ZIF-90-ACE) was prepared and used in the purification of ACE inhibitory peptides from Wakame (Undaria pinnatifida) protein hydrolysate (<5 kDa). The Fe₃O₄@ZIF-90 nanoparticles were prepared by a one-pot synthesis and crude ACE extract from pig lung was immobilized onto it, which exhibited excellent stability and reusability. A novel ACE inhibitory peptide, KNFL (inhibitory concentration 50, IC₅₀ = 225.87 μM) was identified by affinity purification using Fe₃O₄@ZIF-90-ACE combined with reverse phase-high performance liquid chromatography (RP-HPLC) and MALDI-TOF mass spectrometry. Lineweaver–Burk analysis confirmed the non-competitive inhibition pattern of KNFL, and molecular docking showed that it bound at a non-active site of ACE via hydrogen bonds. This demonstrates that affinity purification using Fe₃O₄@ZIF-90-ACE is a highly efficient method for separating ACE inhibitory peptides from complex protein mixtures and the purified peptide KNFL could be developed as a functional food ingredients against hypertension.     

Fabrication of Gelatin-Based Electrospun Composite Fibers for Anti-Bacterial Properties and Protein Adsorption

A major goal of biomimetics is the development of chemical compositions and structures that simulate the extracellular matrix. In this study, gelatin-based electrospun composite fibrous membranes were prepared by electrospinning to generate bone scaffold materials. The gelatin-based multicomponent composite fibers were fabricated using co-electrospinning, and the composite fibers of chitosan (CS), gelatin (Gel), hydroxyapatite (HA), and graphene oxide (GO) were successfully fabricated for multi-function characteristics of biomimetic scaffolds. The effect of component concentration on composite fiber morphology, antibacterial properties, and protein adsorption were investigated. Composite fibers exhibited effective antibacterial activity against Staphylococcus aureus and Escherichia coli. The study observed that the composite fibers have higher adsorption capacities of bovine serum albumin (BSA) at pH 5.32–6.00 than at pH 3.90–4.50 or 7.35. The protein adsorption on the surface of the composite fiber increased as the initial BSA concentration increased. The surface of the composite reached adsorption equilibrium at 20 min. These results have specific applications for the development of bone scaffold materials, and broad implications in the field of tissue engineering.     

Preparation and Characterization of Chitosan Poly(acrylic acid) Magnetic Microspheres

Spherical microparticles, capable of responding to magnetic fields, were prepared by encapsulating dextran-coated Fe₃O₄ nanoparticles into chitosan poly(acrylic acid) (PAA) microspheres template. The obtained magnetic microspheres were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and thermogravimetry (TG). The results showed that the microspheres were formed and demonstrated magnetic behavior in an applied magnetic field. In addition, magnetite particles were well encapsulated and the composite particles have high magnetite content, which was more than 40%.     

Three New and Eleven Known Unusual C25 Steroids: Activated Production of Silent Metabolites in a Marine-Derived Fungus by Chemical Mutagenesis Strategy using Diethyl Sulphate

Three new (1–3) and 11 known (4–14) C25 steroids with an unusual bicyclo[4.4.1]A/B ring system were isolated by tracing newly produced metabolites in the EtOAc extract of an antitumor mutant AD-1-2 obtained by the diethyl sulphate (DES) mutagenesis of a marine-derived Penicillium purpurogenum G59. HPLC-PDAD-UV and HPLC-ESI-MS analyses indicated that the G59 strain did not produce these metabolites and the production of 1–14 in the mutant AD-1-2 extract was caused by the activation of silent metabolites in the original G59 strain by DES mutagenesis. The structures of the new compounds, named antineocyclocitrinols A (1) and B (2) and 23-O-methylantineocyclocitrinol (3), including their absolute configurations were determined by various spectroscopic methods, especially the NMR and Mo₂-induced CD analyses. Compounds 1–3 provide the first examples of the C25 bicyclo[4.4.1]A/B ring steroids with the Z-configuration of 20,22-double bond. All of 1–14 weakly inhibited several human cancer cell lines to varying extents. These results provided additional examples for the successful application of the chemical mutagenesis strategy using DES to discover new compounds by activating silent metabolites in fungal isolates and supported also the effectiveness and usefulness of this new strategy.     

Indole Diterpenoids and Isocoumarin from the Fungus,Aspergillus flavus,Isolated from the Prawn,Penaeus vannamei

Two new indole-diterpenoids (1 and 2) and a new isocoumarin (3), along with the known β-aflatrem (4), paspalinine (5), leporin B (6), α-cyclopiazonic acid (7), iso-α-cyclopiazonic acid (8), ditryptophenaline (9), aflatoxin B₁ (10), 7-O-acetylkojic acid (11) and kojic acid (12), were isolated from the fermentation broth of the marine-derived fungus, Aspergillus flavus OUCMDZ-2205. The structures of Compounds 1–12 were elucidated by spectroscopic analyses, quantum ECD calculations and the chemical method. New Compound 1 exhibited antibacterial activity against Staphylococcus aureus with a MIC value of 20.5 μM. Both new Compounds 1 and 2 could arrest the A549 cell cycle in the S phase at a concentration of 10 μM. Compound 1 showed PKC-beta inhibition with an IC₅₀ value of 15.6 μM. In addition, the absolute configurations of the known compounds, 4–6 and leporin A (6a), were also determined for the first time.     

Microstructure and properties of Ni-Fe3O4 composite plated polyester fabric

In this study, electroless Ni-Fe₃O₄ composite plating on polyester fabric modified with 3-aminopropyltrimethoxysilane (APTMS) was investigated under ultrasonic irradiation. Effects of deposit weight on microstructure and properties of Ni-Fe₃O₄ composite coating were studied. Surface morphology, chemical composition and state, crystal structure of the electroless Ni-Fe₃O₄ composite plated polyester fabric were characterized by SEM, EDX, XPS and XRD. Magnetic properties, electrical resistivity and electromagnetic interference (EMI) shielding effectiveness (SE) of Ni-Fe₃O₄ plated polyester fabric were also evaluated. The presence of co-deposition of Fe₃O₄ in Ni coating on the polyester fabric is demonstrated by an XPS analysis. At a higher deposit weight, there is an increase in particle size and saturation magnetization, and a decrease in electrical resistivity with respect to the rise of deposit weight, respectively. As the Ni-Fe₃O₄ weight on the treated fabric is 32.90 g/m², the EMI SE of the Ni-Fe₃O₄ plated polyester fabric arrives 15–20 dB at frequencies that range from 8 to 18 GHz. The results indicate the Ni-Fe₃O₄ plated polyester fabrics are used as super-paramagnetic, conductive and EMI shielding materials.     

Controlling the Properties of OPEFB/PLA Polymer Composite by Using Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> for Microwave Applications

Microwave-absorptive polymer composite materials provide protection against interference to communication systems caused by microwave-inducing devices. Microwave-absorptive polymer composites were prepared from polylactic acid (PLA) biocomposite blended with oil palm empty fruit bunch (OPEFB) fiber and commercial Iron oxide (Fe₂O₃) as filler using the melt-blending method. The composites characterization was carried out using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses. The coefficient of reflection S₁₁ and coefficient of transmission S₂₁ of the composites for various Fe₂O₃ filler percentages were determined using a rectangular waveguide in connection with microwave vector network analyser (HP/Agilent model PNA N5227). These coefficients were then used to calculate microwave-absorption properties (in decibels). XRD analysis showed that increasing amounts of reinforced material (Fe₂O₃) reduces the crystallinity of the composites. SEM data indicated that Fe₂O₃ filler ratio increased in the composites, and adhesion to the cellulose fiber grew gradually until the highest percentage of filler was added. The complex relative permittivity and relative permeability were obtained within the broad frequency range of 8–12 GHz at room temperature for various percentages of filler and were measured by the transmission/reflection method using a vector network analyser. Fe₂O₃ embedment in OPEFB/PLA was observed to have resulted in enhancing the dielectric and magnetic properties. The values of permittivity and permeability increased with increasing Fe₂O₃ filler content. Theoretical simulation studied the relation between ε′ and ε″ of the relative complex permittivity in terms of Cole-Cole dispersion law. The result indicated that the processes of Debye relaxation in Fe₂O₃/OPEFB/PLA, the unique dielectric characteristics of Fe₂O₃ cannot be accounted for by both the Debye dipolar relaxation and natural resonance. Results further showed that the material transmission, reflection, and absorption properties could be controlled by changing the percentage of Fe₂O₃ filler in the composites.     

Thalassospiramide G,a New γ-Amino-Acid-Bearing Peptide from the Marine Bacterium Thalassospira sp

In the chemical investigation of marine unicellular bacteria, a new peptide, thalassospiramide G (1), along with thalassospiramides A and D (2–3), was discovered from a large culture of Thalassospira sp. The structure of thalassospiramide G, bearing γ-amino acids, such as 4-amino-5-hydroxy-penta-2-enoic acid (AHPEA), 4-amino-3,5-dihydroxy-pentanoic acid (ADPA), and unique 2-amino-1-(1H-indol-3-yl)ethanone (AIEN), was determined via extensive spectroscopic analysis. The absolute configuration of thalassospiramide D (3), including 4-amino-3-hydroxy-5-phenylpentanoic acid (AHPPA), was rigorously determined by ¹H–¹H coupling constant analysis and chemical derivatization. Thalassospiramides A and D (2–3) inhibited nitric oxide (NO) production in lipopolysaccharide (LPS)-stimulated mouse macrophage RAW 264.7 cells, with IC₅₀ values of 16.4 and 4.8 μM, respectively.     

Chemistry and Tumor Cell Growth Inhibitory Activity of 11,20-Epoxy-3Z,5(6)E-diene Briaranes from the South China Sea Gorgonian Dichotella gemmacea

Eighteen new 11,20-epoxy-3Z,5E-dien briaranes, gemmacolides AA–AR (1–18), were isolated together with three known analogs, dichotellides F (19) and I (20), and juncenolide C (21), from the South China Sea gorgonian Dichotella gemmacea. The structures of the compounds were elucidated by detailed spectroscopic analysis and comparison with reported data. The absolute configuration was determined based on the ECD experiment. In the in vitro bioassay, compounds 1–3, 5, 6, 8–12, and 14–19 exhibited different levels of growth inhibition activity against A549 and MG63 cell lines. Preliminary structure-activity analysis suggests that 12-O-isovalerate may increase the activity whereas 13- or 14-O-isovalerate may decrease the activity. Contribution of substitutions at C-2 and C-16 remains uncertain.     

Vibrio vulnificus MO6-24/O Lipopolysaccharide Stimulates Superoxide Anion,Thromboxane B2, Matrix Metalloproteinase-9, Cytokine and Chemokine Release by Rat Brain Microglia in Vitro

Although human exposure to Gram-negative Vibrio vulnificus (V. vulnificus) lipopolysaccharide (LPS) has been reported to result in septic shock, its impact on the central nervous system’s innate immunity remains undetermined. The purpose of this study was to determine whether V. vulnificus MO6-24/O LPS might activate rat microglia in vitro and stimulate the release of superoxide anion (O₂⁻), a reactive oxygen species known to cause oxidative stress and neuronal injury in vivo. Brain microglia were isolated from neonatal rats, and then treated with either V. vulnificus MO6-24/O LPS or Escherichia coli O26:B6 LPS for 17 hours in vitro. O₂⁻ was determined by cytochrome C reduction, and matrix metalloproteinase-2 (MMP-2) and MMP-9 by gelatinase zymography. Generation of cytokines tumor necrosis factor alpha (TNF-α), interleukin-1 alpha (IL-1α), IL-6, and transforming growth factor-beta 1 (TGF-β1), chemokines macrophage inflammatory protein (MIP-1α)/chemokine (C-C motif) ligand 3 (CCL3), MIP-2/chemokine (C-X-C motif) ligand 2 (CXCL2), monocyte chemotactic protein-1 (MCP-1)/CCL2, and cytokine-induced neutrophil chemoattractant-2alpha/beta (CINC-2α/β)/CXCL3, and brain-derived neurotrophic factor (BDNF), were determined by specific immunoassays. Priming of rat microglia by V. vulnificus MO6-24/O LPS in vitro yielded a bell-shaped dose-response curve for PMA (phorbol 12-myristate 13-acetate)-stimulated O₂⁻ generation: (1) 0.1–1 ng/mL V. vulnificus LPS enhanced O₂⁻ generation significantly but with limited inflammatory mediator generation; (2) 10–100 ng/mL V. vulnificus LPS maximized O₂⁻ generation with concomitant release of thromboxane B₂ (TXB₂), matrix metalloproteinase-9 (MMP-9), and several cytokines and chemokines; (3) 1000–100,000 ng/mL V. vulnificus LPS, with the exception of TXB₂, yielded both attenuated O₂⁻ production, and a progressive decrease in MMP-9, cytokines and chemokines investigated. Thus concentration-dependent treatment of neonatal brain microglia with V. vulnificus MO6-24/O LPS resulted in a significant rise in O₂⁻ production, followed by a progressive decrease in O₂⁻ release, with concomitant release of lactic dehydrogenase (LDH), and generation of TXB₂, MMP-9, cytokines and chemokines. We hypothesize that the inflammatory mediators investigated may be cytotoxic to microglia in vitro, by an as yet undetermined autocrine mechanism. Although V. vulnificus LPS was less potent than E. coli LPS in vitro, inflammatory mediator release by the former was clearly more efficacious. Finally, we hypothesize that should V. vulnificus LPS gain entry into the CNS, it would be possible that microglia might become activated, resulting in high levels of O₂⁻ as well as neuroinflammatory TXB₂, MMP-9, cytokines and chemokines.     

Surface modification and ternary system dye removal ability of manganese ferrite nanoparticle

In this paper, the surface of magnetic manganese ferrite nanoparticles (MFN) was modified using cetyl trimethylammonium bromide (CTAB). The modified MFN was studied using Fourier transform infrared spectroscopy (FTIR). The adsorption capacity of surface modified MFN (MFN-CTAB) was investigated for dye removal for single and ternary systems. Three anionic dyes, C.I. Direct Red 80 (DR80), C.I. Direct Red 31 (DR31), and C.I. Acid Blue 92 (AB92), were used as model compounds. The effects of operational parameters on dye removal (i.e. adsorbent dosage, dye concentration and salt) and the kinetic and isotherm of dye adsorption were studied. The adsorption kinetic for the dyes was found to be well described by the pseudo-second order model. The maximum dye adsorption capacity (Q ₀) of MFN-CTAB for DR80, DR31 and AB92 was 83 mg/g, 59 mg/g and 70 mg/g, respectively. The adsorption isotherm data were analyzed using the Langmuir, Freundlich, and Temkin equations. The results revealed that the Langmuir model fitted the adsorption data better. The results showed that the MFN-CTAB as a magnetic adsorbent might be a suitable alternative to remove dyes from colored aqueous solutions.     

Fabrication and Characterisation of Functionalised Superparamagnetic Bacterial Nanocellulose Using Ultrasonic-Assisted <Emphasis Type="Italic">In Situ</Emphasis> Synthesis

Ultrasonic-assisted in situ synthesis was performed using bacterial nanocellulose (BNC) and magnetite nanoparticles (Fe₃O₄ NPs) to synthesise superparamagnetic membranes as BNC/Fe₃O₄ nanocomposite films (BNC/Fe₃O₄ NCFs). Vibrating sample magnetometry of these BNC/Fe₃O₄ NCFs exhibited superparamagnetic properties with high saturation magnetisation at 40.57 emu g^-1. Morphology of BNC/Fe₃O₄ NCFs was studied by field-emission scanning electron microscopy. Results showed Fe₃O₄ NPs with diameter 30 to 50 nm trapped in a BNC structure. Fourier transform infrared spectroscopy analysis confirmed the incorporation of BNC and Fe₃O₄ NPs. Thermal properties of the nanocomposite films increased with Fe₃O₄ NPs in the BNC structure compared with native BNC. Surface wettability of BNC/Fe₃O₄ NCFs was determined by contact angle and revealed hydrophobic properties. Results showed that ultrasonic-assisted in situ synthesis of superparamagnetic BNC/Fe₃O₄ NCFs is an important property when utilising BNC/Fe₃O₄ NCFs with a hydrophobic nonpolar polymeric matrix in electronic device applications.     

Ultrastructure of Fusion Product between Protoplasts from C3 and C4 Species of Amaranthaceae

Summary

This paper describes the ultrastructure of the electric field-induced fusion products of C₃ and C₄ species of Amaranthaceae at the early developmental stage. Protoplasts of C₃ species were isolated from a Ceiosia cristata L. cell suspension and, those of C₄ species were isolated from an Amaranthus tricolor L. cotyledon. Incompatibility occurred in the C₃/C₄ hybrid. The incompatibility reactions were detected in the newly formed hybrid cells accompanied with significant changes in the nucleolus (segregation of nucleolar components) and plastids (cup-like shape or amoeboid plastid enclosing cytoplasmic materials) of C₃ species parent. The structural changes in the organelles of the C₄ partner were less marked. After 5 days of culture, most organelles showed high cellular activity, and a normal dedifferentiation process of mesophyll chloroplasts was observed. At this stage nucleolar segregation was not detected and the C₃ species plastids were difficult to distinguish from the proplastids formed from mesophyll chloroplasts. In addition, some mitochondria showed bursting-like structure. However, under the culture condition used these somatic incompatibility did not seem to impair further growth of fusion products since they were still proliferating well resulting in callus formation.     

Total Synthesis and Biological Activity of Marine Alkaloid Eudistomins Y1–Y7 and Their Analogues

Eudistomin Y class compounds are a series of β-carbolines which was originally isolated from a marine turnicate or ascidian near the South Korea Sea. These compounds contain bromo-substituted groups, which is one of the typical characters of marine natural products. We report herein the chemical synthesis and biological evaluation of seven new β-carboline-based metabolites, Eudistomins Y₁–Y₇, and their hydroxyl-methylated phenyl derivatives. Using bromo-substituted tryptamines and bromo-substituted phenylglyoxals as the key intermediates, Eudistomins Y₁–Y₇ and their derivatives were synthesized via the acid-catalyzed Pictet-Spengler reaction and fully characterized by ¹H- and ¹³C-NMR and mass spectroscopy. Biological studies revealed that all of the compounds showed moderate growth inhibitory activity against breast carcinoma cell line MDA-231 with IC₅₀ of 15–63 μM and the inhibitory activities of hydroxyl-methylated phenyl products were higher than that of the corresponding natural products Eudistomins Y₁–Y₇.     

Alkaloids from the Mangrove-Derived Actinomycete Jishengella endophytica 161111

A new alkaloid, 2-(furan-2-yl)-6-(2S,3S,4-trihydroxybutyl)pyrazine (1), along with 12 known compounds, 2-(furan-2-yl)-5-(2S,3S,4-trihydroxybutyl)pyrazine (2), (S)-4-isobutyl-3-oxo-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-6-carbaldehyde (3), (S)-4-isopropyl-3-oxo-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-6-carbaldehyde (4), (4S)-4-(2-methylbutyl)-3-oxo-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-6-carbaldehyde (5), (S)-4-benzyl-3-oxo-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazine-6-carbaldehyde (6), flazin (7), perlolyrine (8), 1-hydroxy-β-carboline (9), lumichrome (10), 1H-indole-3-carboxaldehyde (11), 2-hydroxy-1-(1H-indol-3-yl)ethanone (12), and 5-(methoxymethyl)-1H-pyrrole-2-carbaldehyde (13), were isolated and identified from the fermentation broth of an endophytic actinomycetes, Jishengella endophytica 161111. The new structure 1 and the absolute configurations of 2–6 were determined by spectroscopic methods, J-based configuration analysis (JBCA) method, lactone sector rule, and electronic circular dichroism (ECD) calculations. Compounds 8–11 were active against the influenza A virus subtype H1N1 with IC₅₀ and selectivity index (SI) values of 38.3(±1.2)/25.0(±3.6)/39.7(±5.6)/45.9(±2.1) μg/mL and 3.0/16.1/3.1/11.4, respectively. The IC₅₀ and SI values of positive control, ribavirin, were 23.1(±1.7) μg/mL and 32.2, respectively. The results showed that compound 9 could be a promising new hit for anti-H1N1 drugs. The absolute configurations of 2–5, ¹³C nuclear magnetic resonance (NMR) data and the specific rotations of 3–6 were also reported here for the first time.