Controllable Preparation of Plasmonic Gold Nanostars for Enhanced Photothermal and SERS Effects

Gold nanostars(Au NSs) are asymmetric anisotropic nanomaterials with sharp edge structure. As a promising branched nanomaterial, Au NS has excellent plasmonic absorption and scattering properties. In order to tune the plasmonic photothermal and surface-enhanced Raman scattering(SERS) activity of Au NSs to obtain the desired characteristics, the effects of reagents on the local surface plasmon resonance(LSPR) bands of Au NSs were studied and the morphology and size were regulated. Nanoparticles with different sharp edges were synthesized to make their local plasmon resonance mode tunable in the visible and near-infrared region. The effects of the number and sharpness of different tips under the control of AgNO₃ on the photothermal response of Au NSs and the SERS activity and their mechanism were discussed in detail. The results show that as the length of the branch tip becomes longer and the sharpness increases, the plasmonic photothermal effect of Au NSs is strengthened, and the photothermal conversion efficiency is the highest up to 40% when the length of Au NSs is the longest. Au NSs with high SERS activity are used for the Raman detection substrate. Based on this property, the quantitative detection of the pesticide thiram is achieved.     

Analysis in protein profile,antioxidant activity and structure-activity relationship based on ultrasound-assisted liquid-state fermentation of soybean meal with Bacillus subtilis

This study investigated effects of ultrasound on the contents of peptide and soluble protein, antioxidant activity, functionalities and structural characteristics of fermented soybean meal (FSBM) with Bacillus subtilis systematically. The results showed that there were significant effects of ultrasound treatments (frequency, treatment time and power density) on the contents of peptide and soluble protein (p < 0.05). Under the optimum ultrasound conditions (power density of 0.08 W/mL, frequency of 33 kHz and treatment time of 1 h) by single factor experiment, the contents of peptide and soluble protein increased by 31.27% and 18.79% compared to those of the control, respectively. Additionally, the in vitro antioxidant activity (•OH scavenging rate, Fe²⁺ chelating capacity and DPPH radical scavenging rate) and functional properties (emulsifying activity and emulsifying stability) of FSBM were found to be noticeably improved by ultrasound (p < 0.05). The fourier transform infrared (FTIR) spectroscopy revealed that ultrasound caused protein molecules to unfold with a decrease content of α-helix and β-turn and an increase in the proportion of β-sheet and random coil. Besides, atomic force microscope (AFM) results indicated that ultrasonication generally increased the surface roughness of protein and the protein sonicated with higher frequency (≥33 kHz) exhibited a greater height compared to lower frequency ultrasonication. Structure-activity relationship analysis illustrated that there was a good linear relationship between •OH scavenging rate and β-sheet/β-turn with Pearson’s correlation coefficient r of −0.86/0.90. Collectively, the selection of ultrasonic parameters is essential for the preparation of functional protein and bioactive peptide by enhancing fermentation of agroindustrial by-products.     

Synergistic antibacterial effects of ultrasound and thyme essential oils nanoemulsion against Escherichia coli O157:H7

Essential oil nanoemulsions have been proven to have stronger antimicrobial effects compared to the essential oil alone or coarse emulsion. Sonoporation could be the promising candidate to trigger a synergistic effect with thyme essential oil nanoemulsion (TEON) and produce a more effective antibacterial efficacy. Therefore, in this study, the bactericidal effects of ultrasound (US) in combination with TEON treatments against Escherichia coli (E. coli) O157:H7 were investigated. The remarkable synergistic effects of US (20 kHz, 255 W/cm², 9 min) and TEON (0.375 mg/mL) treatments at 22 °C reduced E. coli O157:H7 populations by 7.42 ± 0.27 log CFU/mL.The morphological changes of cells exposed to different treatments were observed by scanning electron microscopy and transmission electron microscopy. The results showed that the synergistic effects of the ultrasound and TEON treatments altered the morphology and interior microstructure of organism cells. Laser scanning confocal microscopy (LSCM) images revealed that the combination treatments of ultrasound and TEON altered the permeability of cell membranes, and this affected the integrity of E. coli O157:H7 cells. This was further indicated by the high amounts of nucleic acids and proteins released from these cells following treatment.The results from this study illustrated the mechanisms of the synergistic effects of sonoporation and TEON treatments and provided valuable information for their potential in food pasteurization.     

Magnetite nanoparticles−based hydroxyl radical scavenging activity assay of antioxidants using N,N-dimethyl-p-phenylenediamine probe

Excessive amounts of reactive oxygen species (ROS), unless counterbalanced by antioxidants, can cause cellular damage under oxidative stress conditions; therefore, antioxidative defenses against ROS must be measured. With the development of nanotechnology, nanoparticles have found numerous applications in science, health, and industries. Magnetite nanoparticles (Fe ₃ O ₄ :MNPs) have attracted attention because of their peroxidase-like activity. In this study, hydroxyl radicals (•OH) generated by MNPs-catalyzed degradation of H ₂ O ₂ converted the N,N-dimethyl-p-phenylenediamine (DMPD) probe into its colored DMPD•+ radical cation, which gave an absorbance maximum at λ = 553 nm. In the presence of antioxidants, •OH was partly scavenged by antioxidants and produced less DMPD• ⁺ , causing a decrease in the 553 nm-absorbance. Antioxidant concentrations were calculated with the aid of absorbance differences between the reference and sample solutions. The linear working ranges and trolox equivalent antioxidant capacity coefficients of different classes of antioxidants were determined by applying the developed method. In addition, binary and ternary mixtures of antioxidants were tested to observe the additivity of absorbances of mixture constituents. The method was applied to real samples such as orange juice and green tea. Student t-test, F tests, and the Spearman’s rank correlation coefficient were used for statistical comparisons.     

Antibacterial triterpenoids from the leaves of Ilex hainanensis Merr.

One new triterpenoid (1) and seven known analogues (2–8) were isolated from the leaves of Ilex hainanensis Merr.. Their structures were established by analysis of their MS, 1D and 2D NMR spectroscopic data and comparison with those in the literature. The antibacterial activity of compounds 1–8 were evaluated by determination of minimum inhibitory concentration using twofold microdilution broth method against Streptococcus mutans ATCC 25175 (Gram-positive) and Fusobacterium nucleatum ATCC 10953 (Gram-negative). Compounds 3 and 5 showed significant antibacterial activity against S. mutans in concentration of 9.7 μg/mL, while showed little antibacterial activity against F. nucleatum. On the contrary, the inhibitory activity of compounds 1, 2 and 6 against F. nucleatum were higher than them against S. mutans.     

Facile synthesis,characterization, and decolorization activity of Mn2+ and Al3+ co-doped hexagonal-like ZnO nanostructures as photocatalysts

A good photocatalyst with high efficiency can be synthesized easily using eco-friendly materials and processes. Our synthesized samples exhibit all of the aforementioned features. In this work, manganese co-doped ZnO at different weight percentages (3, 6, 9, and 15 wt.%) with and without 1.5 wt.% aluminum was synthesized by hydrothermal method, and their photocatalytic activity in aqueous solutions of methyl orange (MO) was investigated under visible light. The structural and optical properties of the samples were characterized using X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and diffuse reflectance spectroscopy. In this work, Mn²⁺ ions in the 9%Mn/ZnO sample and Mn²⁺, Al³⁺ ions in the (9%Mn, 1.5%Al)/ZnO sample calcined at 800 °C were replaced instead with some Zn²⁺ ions in hexagonal wurtzite structures of ZnO. These structures were found next to each other in the form of a hexagonal shape that created 3D-hexagonal-like ZnO nanostructures. Finally, nanoparticles (NPs) and nano hexagonal-like ZnO nanostructures were, respectively, dispersed on the surface of 3D-hexagonal-like structure of 9%Mn/ZnO and (9%Mn, 1.5%Al)/ZnO. Diffuse reflectance spectroscopy analysis showed that the (9%Mn, 1.5%Al)/ZnO sample had more light absorption than 9%Mn/ZnO. However, contrary to our expectations, the 9%Mn/ZnO sample had better decolorization efficiency (94%) after 60 min under visible light, which could be attributed to a significant increase in the level of recombination by the aluminum ions.     

Tridentate Schiff base and 4,4′-bipyridine coordinated di/polynuclear Cu (II) complexes: Synthesis,crystal structure,DNA/protein binding and catecholase activity

4,4′-bipyridine bridged two Cu (II) complexes, [Cu₂L¹₂(4,4′-bipy)(H₂O)₂](ClO₄)₂ ( 1 ) and [Cu₂L²₂(4,4′-bipy)]_n·(2H₂O)_n ( 2 ) (where, HL¹ = 2-[(3-methylamino-propylimino)-methyl]-phenol, H₂L² = 3-[(2-hydroxy-3-methoxy-benzylidene)-amino]-propionic acid, and 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by single crystal structure determination, mass spectrometry, FT-IR, electronic absorption, and emission spectroscopy. Complex 1 is dinuclear cationic compound and counter balanced by perchlorate anion, whereas complex 2 possesses 1D poly-nuclear structure. Both the complexes crystallize in monoclinic system with P2₁/c space group and the copper centers possess square pyramidal geometry. H-bonding, C-H···π, π···π interactions results the formation of two dimentional supramolecular structure for both the complexes. Interactions of complexes with bovine serum albumins (BSA) and human serum albumins (HSA) have been studied by using electronic absorption and emission spectroscopic technique. The calculated values of binding constants (K_b) are (9.22 ± 0.26) × 10⁵ L mol⁻¹ ( 1 -BSA), (7.19 ± 0.16) × 10⁵ L mol⁻¹ ( 1 -HSA), (5.05 ± 0.20) × 10⁵ L mol⁻¹ ( 2 -BSA) and (3.56 ± 0.25) × 10⁵ L mol⁻¹ ( 2 -HSA). The mechanism of serum albumins-complex interactions have been investigated by fluorescence lifetime measurement. Fluorescence spectroscopic studies indicate that both the complexes interact with calf thymas-DNA. Catecholase activity of the complexes has been studied in methanol using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate and the result show that both the complexes are active for catalytic oxidation of 3,5-DTBC to 3,5-di-tert-butylquinone (3,5-DTBQ) in presence of molecular oxygen. Calculated values of turnover numbers are 71.81 ± 1.04 h⁻¹ and 69.45 ± 0.74 h⁻¹ for 1 and 2 , respectively.     

Transition metal complexes of Schiff base ligand based on 4,6-diacetyl resorcinol

Novel Schiff base ligand based on the condensation of 4,6-diacetyl resorcinol with 2-amino-4-methylthiazole in addition to its metal complexes with Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II), Zn (II) and Cd (II) ions have been synthesized. The structure, electronic properties, and thermal behaviour of Schiff base and its metal complexes have been studied by elemental analysis, mass, ¹H NMR, IR spectra, thermal analysis, and theoretically by density function theory. The ligand acted as mononegative bidentate (NO) ligand and all complexes showed octahedral geometry except Cu (II) showed tetrahedral geometry as indicated from the spectral and magnetic studies. The Cu (II), Zn (II) and Cd (II) complexes were non electrolytes while the rest of the complexes were electrolytes. The antibacterial plus anticancer activities of the parent Schiff base and its metal complexes were screened. In addition, the molecular docking study was performed to explore the possible ways for binding to Crystal Structure of Human Astrovirus capsid protein (5ibv) receptor.     

Synthesis,Characterization and Evaluation of the Antibacterial and Antitumor Activity of HalogenatedSalen Copper (II) Complexes derived from Camphoric Acid

Platinum metal complexes are the most common chemotherapeutics currently used in cancer treatment. However, the frequent adverse effects, as well as acquired resistance by tumor cells, urge the development of effective alternatives. In the recent past, copper complexes with Schiff base ligands have emerged as good alternatives, showing interesting results. Accordingly, and in continuation of previous studies in this area, three new camphoric acid-derived halogenated salen ligands and their corresponding Cu (II) complexes were synthesized and their antitumor activity was evaluated in order to determine the influence of the type and number of halogens present (Br, Cl). The in vitro cytotoxic activity was screened against colorectal WiDr and LS1034 and against breast MCF-7 and HCC1806 cancer cell lines. The results proved the halogenated complexes to be very efficient, the tetrachlorinated Cu (II) complex being the most promising, presenting IC₅₀ of 0.63–1.09 μM for the cell lines studied. The complex also shows selectivity to colorectal cancer cells compared to non-tumor colon cells. It is worth highlighting that the tetrachlorinated Cu (II) complex, our most efficient complex, shows a significantly more powerful antitumor effect than the reference drugs currently used in conventional chemotherapy. The halogenated salen and corresponding complexes were also screened for their antimicrobial activity against four bacterial species-Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa-and four fungal species-Candida albicans, Candida glabrata, Aspergillus fumigatus and Alternaria alternata. The compounds were found to exhibit moderate to strong antibacterial activity against the bacterial strains studied. NMR studies and theoretical calculations provided some insight into the structure of the ligands and copper complexes. Considering the results presented herein, our work validates the potential use of copper-based chemotherapeutics as alternatives for cancer treatment.     

Synthesis,characterization, and biological investigation of new mixed-ligand complexes

A novel series of mixed-ligand complexes of 5,5′-{(1E,1E′)-1,4-phenelynebis(diazene-2,1-diyl)}bis(quinolin-8-ol) (H₂L₁) as a primary ligand and 4-aminoantipyrine(L₂) as a secondary ligand with Mn(II) ion were prepared using two general formulae: [Mn₂(H₂L₁)₂(L₂)₂X₄].4Cl (X = OH₂( 1 ), ONO₂⁻( 2 ), Cl=nil; OAc( 3 ), Cl = nil) and [Mn₂(H₂L₁)(L₂)₂(O₂SO₂)₂]( 4 ). Free ligands and their complexes were characterized. Electronic absorption spectra of the mixed-ligand complexes indicate a distorted octahedral geometry around the central metal ion, and the anions X⁻ are in the axial positions for all compounds. The ligands behave in a neutral bidentate manner, through nitrogen atoms and oxygen atoms of the carbonyl group (L₂), whereas H₂L₁ coordinated through nitrogen and OH groups as a neutral bidentate ligand. All complexes do not contain coordinated water molecules, but complex ( 1 ) contains four water molecules. The water molecules are removed in a single step. The complexes exhibited magnetic susceptibility corresponding to five unpaired electrons. The antimicrobial activity of the Mn(II) mixed-ligand complexes ( 1–4 ) against two gram-positive bacteria, three local gram-negative bacteria, and three fungi species was tested. Mn(II) mixed-ligand complex ( 2 ) exhibited significant antibacterial activity against Bacillus cereus, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, and Pseudomonas sp. Mixed-ligand complex ( 2 ) exhibited a high potential cytotoxicity against the growth of human lung cancer cells.