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Royal Society of Chemistry
RSC Advances

Royal Society of Chemistry

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    A pair of 2D chiral Ag(i) enantiomers with dual chiral elements: syntheses, structures, and photoluminescent and chiroptical properties

    Cui, MinghuiWang, Ai-LingLiu, YingfanXiao, Hongping...
    7页
    查看更多>>摘要：In this work, two new enantiopure bis-monodentate N-donor chiral ligands, namely (-)/(+)-2-(4 '-pyridyl)-4,5-pinene-pyridine (L-R/L-S), have been designed and synthesized. Using L-R and L-S as bridging ligands to react with AgClO4, a pair of novel 2D chiral Ag(i) enantiomers formulated as [Ag-2(L-R)(2)(ClO4)(2)](n) (R-1) and [Ag-2(L-S)(2)(ClO4)(2)](n) (S-1) were isolated and characterized. In R-1 and S-1, each Ag(i) ion is bonded by two N atoms from two different chiral L-R or L-S ligands, leading to the formation of 1D right- or left-handed -L-Ag(i)-L- helical chains. Moreover, two adjacent helical chains are further doubly linked by two monodentate ClO4- anions through weak Ag-O contacts to form 2D network structures, in which dual chiral elements, i.e., center chirality and helical chirality coexist. Interestingly, each free ligand L-R/L-S and R-1/S-1 enantiomers show very different ECD spectra in the solid state and in solution, which are correlated to the intermolecular interactions and molecular structures in each state, respectively. Notably, as a representative, R-1 exhibits intense room temperature photoluminescence both in the solid state and in solution with different emission features and mechanisms, while it also shows more intense emission than that of free ligand L-R. In particular, R-1 and S-1 represent the first examples of 2D Ag(i) chiral coordination polymers (CCPs) supported by ClO4- anions, possessing dual chiral elements.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Highly fluorescent aryl-cyclopentadienyl ligands and their tetra-nuclear mixed metallic potassium-dysprosium clusters

    Arumugam, SelvakumarReddy, Pulikanti GuruprasadFrancis, MariaKulkarni, Aditya...
    7页
    查看更多>>摘要：Two alkyl substituted triaryl-cyclopentadienyl ligands [4,4 '-(4-phenylcyclopenta-1,3-diene-1,2-diyl)bis(methylbenzene) (1) and 4,4 ',4 ''-(cyclopenta-1,3-diene-1,2,4-triyl)tris(methylbenzene) (2)] have been synthesized via cross-aldol condensation followed by Zn-dust mediated cyclization and acid catalyzed dehydration reactions. The fluorescence properties of 1 and 2 have been studied in solution and solid state. The ligands exhibited aggregation-induced emission enhancement (AIEE) in THF/water solution. 1 and 2 have been found to be significantly more fluorescent in the solid state than in their respective solutions. This phenomenon can be attributed to the strong intermolecular CHMIDLINE HORIZONTAL ELLIPSIS pi interactions present in 1 and 2 which leads to the tight packing of molecules in their solid-state. Both 1, 2 and their corresponding anions have been studied by theoretical calculations. Ligands 1 and 2 have been shown to react with anhydrous DyCl3 in the presence of potassium metal at high temperature to afford two fluorescent chloride-bridged tetra-nuclear mixed potassium-dysprosium metallocenes [(Me2Cp)(4)(Dy2Cl4K2)-Cl-III]center dot 3.5(C7H8) (5) and [(Me3Cp)(4)(Dy2Cl4K2)-Cl-III]center dot 3(C7H8) (6), respectively in good yields.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Colloidal stability and catalytic activity of cerium oxide nanoparticles in cell culture media

    Ju, XiaohuiFucikova, AnnaSmid, BretislavNovakova, Jaroslava...
    12页
    查看更多>>摘要：One of the biggest challenges for the biomedical applications of cerium oxide nanoparticles (CeNPs) is to maintain their colloidal stability and catalytic activity as enzyme mimetics after nanoparticles enter the human cellular environment. This work examines the influences of CeNP surface properties on their colloidal stability and catalytic activity in cell culture media (CCM). Near-spherical CeNPs stabilized via different hydrophilic polymers were prepared through a wet-chemical precipitation method. CeNPs were stabilized via either electrostatic forces, steric forces, or a combination of both, generated by surface functionalization. CeNPs with electrostatic stabilization adsorb more proteins compared to CeNPs with only steric stabilization. The protein coverage further improves CeNPs colloidal stability in CCM. CeNPs with steric polymer stabilizations exhibited better resistance against agglomeration caused by the high ionic strength in CCM. These results suggest a strong correlation between CeNPs intrinsic surface properties and the extrinsic influences of the environment. The most stabilized sample in CCM is poly(acrylic acid) coated CeNPs (PAA-CeNPs), with a combination of both electrostatic and steric forces on the surface. It shows a hydrodynamic diameter of 15 nm while preserving 90% of its antioxidant activity in CCM. PAA-CeNPs are non-toxic to the osteoblastic cell line SAOS-2 and exhibit promising potential as a therapeutic alternative.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    The structural composition of components contributes to the superiority of the geoherb Alisma orientale for "diuresis and diffusing dampness"

    Li, RuLi, Zhi-liChen, Ya-pingBu, Wei-quan...
    11页
    查看更多>>摘要：The purpose of this study is to explore the intrinsic reasons for the superiority of the salt-made geoherb Alisma orientale via comparing the content of various components of the salt-made geoherb Alisma orientale. The effects of "diuresis and diffusing dampness" using salt-made Alisma orientale from seven different origins were investigated through pharmacodynamic experiments in vivo and in vitro. The results indicated that salt-made Alisma orientale from different origins had diuretic efficacy; this was demonstrated by the significant increase in the volume of rat urine, the concentration of Na+, K+, and Cl- in the urine, and the significant decrease in the levels of AQP-2 in rat renal medulla and HK-2 cells. It was also revealed that the diuretic effect of salt-made Alisma orientale from Fujian Province is stronger than those from other provinces. Moreover, the main components and their proportions in the salt-made Alisma orientale samples were further analyzed via principal component analysis. The results showed that alisol A 24-acetate, alisol B, and 23-acetyl alisol B are the main components of salt-made Alisma orientale, and the optimal structural ratio of alisol A 24-acetate, alisol B, and 23-acetyl alisol B was found to be 5.38 : 14.34 : 11.31 via optimizing the ratios of the three main components. It is worth noting that the optimal ratio of the three main components after optimization is the closest to the ratio of the three main components in salt-made Alisma orientale from Fujian Province. This paper reveals the "mystery" of the content ratio of the main active components and its effect on the efficacy, and showed that the proportional relationship between the content of multiple components is the key to their interactions. Therefore, this method of evaluating the quality of salt-made Alisma orientale is obviously reliable, and this study lays the foundations for quality evaluation of salt-made Alisma orientale and other herb slices.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Impact of heavy metals on Ciconia boyciana feathers and Larus saundersi egg shells in the Yellow River delta estuary

    Yang, YueweiLi, JingZhang, FengjiaoSun, Fengfei...
    10页
    查看更多>>摘要：In this study, the Ciconia boyciana and Larus saundersi, typical wetland birds in the Yellow River estuary, were selected as research objects. The feathers and egg shells of Ciconia boyciana and Larus saundersi were collected to determine the contents of heavy metals Cd, Cr, Cu, Zn, Mn, Ni and Pb in the samples. Correlation analysis (CA), principal component analysis (PCA), principal factor analysis (PFA) and potential ecological risk index (RI) were used to analyse and treat the measured heavy metal content data to determine the heavy metal pollution status, source and potential ecological risk in the Yellow River estuary. The results of CA, PCA and PFA showed that the content of Cd in the Yellow River estuary was much higher than the background value and its pollution was the most serious. Cr pollution was second and Mn pollution was the lowest. Heavy metal pollution mainly came from human activities such as oil exploitation, industrial production, use of pesticides and fertilizers, and the pollution caused by natural sources was relatively low. Based on the RI value of heavy metals in the study area, heavy metal Cd had an extremely high ecological risk status, and other heavy metals were all low. The results of this study can provide some reference and theoretical support for bird protection, heavy metal pollution control and ecological restoration in the Yellow River delta.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Structure, microstructure and magnetic investigation of the hexagonal delta-FeSe nanophase produced by mechanochemical synthesis

    Ulbrich, K. F.Paes, V. Z. C.Geshev, J.Campos, C. E. M....
    7页
    查看更多>>摘要：We present a systematic structural, microstructural and magnetic characterization of the hexagonal delta-FeSe nanophase produced by a simple one-step mechanochemical synthesis route, by using conventional X-ray powder diffraction (XRPD), Rietveld refinement, transmission electron microscopy (TEM) and magnetometry techniques. We observed the simultaneous formation of tetragonal beta-FeSe and delta-FeSe after 3 h of milling (with minor amounts of unreacted iron), followed by complete beta-FeSe -> delta-FeSe phase transition as milling time increases to 6 h (no unreacted iron). The average crystallite size of the delta-FeSe phase of about 16 nm after 3 h milling time decreases by about 31% up to the final milling time (24 h). TEM images and electron diffraction patterns confirm the nanometric size of the crystalline domains in the irregularly-shaped agglomerated particles. Two ferromagnetic phases with distinct coercivity spectra were assumed here by considering an assembly of randomly-oriented weakly-anisotropic ferromagnetic particles, mixed at a 4 to 6 volume ratio with other randomly-oriented ferromagnetic grains. Four years after synthesis, the aged samples milled for less than 9 h revealed a certain amount of the beta-FeSe phase that slightly affects the delta-FeSe (micro)structure but causes some variations (decreasing) in magnetic parameters. Milling times as long as 12 h were shown to be necessary to guarantee the delta-FeSe nanophase stability and to retain its magnetic properties over time.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Cellulose hydrolysis using ionic liquids and inorganic acids under dilute conditions: morphological comparison of nanocellulose

    Jordan, Jacobs H.Easson, Michael W.Condon, Brian D.
    12页
    查看更多>>摘要：The preparation of cellulose nanocrystals (CNCs) from cellulose extracted from cotton gin motes (CGM) using an ionic liquid (1-butyl-3-methylimidazolium chloride, [BMIm]Cl) under dilute conditions is reported. The concurrent process involves minimal swelling of cellulose with an ionic liquid and hydrolysis of the cellulose initiated by the addition of either phosphoric (H3PO4), hydrochloric (HCl), or sulfuric (H2SO4) acid. The obtained nanocrystals had similar physical properties (e.g. crystallinity) to the counterparts prepared under conventional conditions and exhibited superior thermal properties for sulfate CNCs. Additionally, the obtained CNCs had low surface functionalization, yet were colloidally stable for >90 days, which is a desirable trait for post-functionalization of CNCs. This process represents a general strategy utilizing dilute ionic liquids in the preparation of nanocellulose under mildly acidic conditions.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    Analysis of Xinjiang asphaltenes using high precision spectroscopy

    Qiyong, XiongWyclif, KiyingiJingjun, PanXiong, Ruiying...
    9页
    查看更多>>摘要：Asphaltenes are known for causing flow assurance problems in numerous oil fields. In this study we present a comparative spectroscopic analysis of Xinjiang heavy oil asphaltenes as part of ongoing research for an environmentally friendly and cheap chemical inhibitor. The goal is to predict the internal morphology of these asphaltenes through comparative analysis using high precision spectroscopy. Fourier transform infrared spectroscopy (FTIR), proton-nuclear magnetic resonance (H-NMR) and electrospray ionization Fourier transform ion cyclotron resonance combined with mass spectroscopy were used in this analysis. Several studies have demonstrated the enormous potential of these techniques to characterize hydrocarbons. Here we comparatively apply these techniques to characterize Xinjiang asphaltenes with reference to earlier imaging studies with atomic force and scanning tunneling microscopy to assign a structure to these asphaltenes. Results revealed the nature of the asphaltenes to be polycyclic, aromatic with both heteroatomic and metallic content. Thirteen basic and eleven non-basic/acidic nitrogen compounds fused within the aromatic network were identified. The mass distribution is in the range between 100-800 Da. H-NMR revealed various structural parameters (aromaticity and degree of unsaturation) and together with FTIR various functional groups were identified that include: ethers, sulphides, amides and sulfoxides. The predicted structures are consistent with the "island" and "aryl linked core" models.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    'Hairy' root extracts as source for 'green' synthesis of silver nanoparticles and medical applications

    Kobylinska, NataliaShakhovsky, AnatolijKhainakova, OlenaKlymchuk, Dmytro...
    13页
    查看更多>>摘要：The research was focused on the synthesis of silver nanoparticles (AgNPs) using extracts from the "hairy" root cultures of Artemisia tilesii Ledeb. and Artemisia annua L. The effect of operational parameters such as type of solvent, temperature of extraction, flavonoids concentration, and reducing power of the wormwood "hairy" root extracts on the particle size and yield of the resultant nanoparticles is reported for the first time. From the studied solvents, a water-ethanol mixture with a concentration of 70 vol% was found to be the best for the extraction of flavonoids from all "hairy" root cultures. The total flavonoid contents in A. annua and A. tilesii "hairy" root extracts were up to 80.0 +/- 0.9 and 108 +/- 4.4 mg RuE per g DW, respectively. Identification of flavonoids was confirmed by UPLC-ESI-UHR-Qq-TOF-MS analysis. Luteolin-7-beta-d-glucopyranosid, isorhamnetin 3-O-glucoside, baicalein-7-O-glucuronide, apigenin-7-O-glucoside, quercetin, sitosterol, caffeoylquinic, galic, chlorogenic and caffeic acids were founded in the extracts. These extracts demonstrated the high reducing activities. Spherical, oval and triangular nanoparticles with effective sizes of 5-100 nm were observed. The TEM data revealed great differences in the shapes of NPs, obtained from the extracts from different root clones. The clustered and irregular NPs were found in the case of using ethanol extracts, mostly aggregated and having the size of 10-50 nm. The sizes of AgNPs decreased to 10-30 nm in the case of using aqueous extracts obtained at 80 degrees C. Biosynthesized AgNPs showed surface plasmon resonance in the range of 400-450 nm. The antimicrobial activity of the as-produced AgNPs was studied by disc diffusion method on Gram-positive (Staphylococcus aureus ATCC 25923 (F-49)), Gram-negative (Pseudomonas aeruginosa ATCC 27853 (F-51), Escherichia coli ATCC 25922 (F-50)) and Candida albicans ATCC 88-653 strains. It was found that the nanoparticles in some cases possessed the greater ability to inhibit microorganism growth compared to 1 mM AgNO3 solution. The colloidal solutions of the obtained AgNPs were stable in the dark for 12 months at room temperature. Thus, the A. annua and A. tilesii "hairy" root extracts can be used for obtaining of bioactive AgNPs.
      原文链接:
    • NSTL
    • Royal Soc Chemistry

    One-step synthesis of Ni(OH)(2)/MWCNT nanocomposites for constructing a nonenzymatic hydroquinone/O-2 fuel cell

    Wu, YuanYang, XiaonanLiu, ShuhuiXing, Yonglei...
    8页
    查看更多>>摘要：In this work, a H-type hydroquinone/O-2 fuel cell was assembled and shows high energy density in neutral phosphate buffer solution at moderate temperature. The anodic material, Ni(OH)(2)/MWCNTs, was synthesized by a one-step hydrothermal synthesis method to oxidize hydroquinone. The cathode material, Pt/MWCNTs, was obtained by an electrodeposition method, and shows great oxygen reduction reaction (ORR) activity. The properties and the morphology of Ni(OH)(2)/MWCNT nanocomposites were characterized by TEM, XPS, EDS-mapping and electrochemical methods, like cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that Ni(OH)(2)/MWCNTs can effectively oxidize hydroquinone and play a dominant role in enhancing the fuel cell performance. The nonenzymatic fuel cell possesses a high power density of 0.24 mW cm(-2) at a cell potential of 0.49 V.
      原文链接:
    • NSTL
    • Royal Soc Chemistry