Design and fabrication of enhanced corrosion resistance Zn-Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys

NASA Astrophysics Data System (ADS)

Zhou, Meng; Yan, Luchun; Ling, Hao; Diao, Yupeng; Pang, Xiaolu; Wang, Yanlin; Gao, Kewei

2017-05-01

Layered double hydroxides (LDHs) with brucite-like layer structure and the facile exchangeability of intercalated anions had attracted tremendous interest in many fields because of their great importance for both fundamental studies and practical applications. Herein zinc-aluminum layered double hydroxides (Zn-Al LDHs) films intercalated with nitrate anions on the magnesium alloy substrate were designed and fabricated via a facile hydrothermal crystallization method. In order to obtain better corrosion resistance, chloride and vanadate anions were intercalated into the LDHs interlayers via the anion-exchange reaction. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were used to examine structure, composition and morphology of the Zn-Al-NO3 LDHs, Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films. The corrosion resistance of the Zn-Al LDHs with different anion films was estimated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurement. EIS and polarization curves measurements revealed that the magnesium alloy could be effectively protected by the Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films due to the blocking effect of chloride anions and the control-release ability of vanadate anions.

The Effect of Single, Binary and Ternary Anions of Chloride, Carbonate and Phosphate on the Release of 2,4-Dichlorophenoxyacetate Intercalated into the Zn-Al-layered Double Hydroxide Nanohybrid

NASA Astrophysics Data System (ADS)

Hussein, Mohd Zobir; Jaafar, Adila Mohamad; Yahaya, Asmah Hj.; Zainal, Zulkarnain

2009-11-01

Intercalation of beneficial anion into inorganic host has lead to an opportunity to synthesize various combinations of new organic-inorganic nanohybrids with various potential applications; especially, for the controlled release formulation and storage purposes. Investigation on the release behavior of 2,4-dichlorophenoxyacetate (2,4-D) intercalated into the interlayer of Zn-Al-layered double hydroxide (ZAN) have been carried out using single, binary and ternary aqueous systems of chloride, carbonate and phosphate. The release behavior of the active agent 2,4-D from its double-layered hydroxide nanohybrid ZANDI was found to be of controlled manner governed by pseudo-second order kinetics. It was found that carbonate medium yielded the highest accumulated release of 2,4-D, while phosphate in combination with carbonate and/or nitrate speeds up the release rate of 2,4-D. These results indicate that it is possible to design and develop new delivery system of latex stimulant compound with controlled release property based on 2,4-D that is known as a substance to increase latex production of rubber tree, Hevea brasiliensis.

Hybrid magnetic materials formed by ferritin intercalated into a layered double hydroxide

NASA Astrophysics Data System (ADS)

Clemente-León, Miguel; Coronado, Eugenio; Primo, Vicent; Ribera, Antonio; Soriano-Portillo, Alejandra

2008-12-01

A hybrid magnetic material formed by ferritin intercalated into a layered double hydroxide (LDH) of Mg and Al (Mg/Al molar ratio 2) is prepared and characterized through powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, electron probe microanalysis (EPMA) and high resolution transmission electron microscopy (HRTEM). One observes an enhancement in the thermal stability of the ferritin molecules when they are inserted in the layered material. Magnetic measurements of the hybrid material exhibit the typical superparamagnetic behaviour of the ferritin molecule. On the other hand, the intercalation of ferritin into the LDH guarantees a homogeneous dispersion of the ferritin molecules, which do not aggregate even after calcination of the sample. This feature allows obtaining well-dispersed magnetic metal oxide nanoparticles upon calcination of the hybrid material.

Synthesis, characterization, and efficacy of antituberculosis isoniazid zinc aluminum-layered double hydroxide based nanocomposites

PubMed Central

Saifullah, Bullo; El Zowalaty, Mohamed Ezzat; Arulselvan, Palanisamy; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin Mahler; Hussein, Mohd Zobir

2016-01-01

The chemotherapy for tuberculosis (TB) is complicated by its long-term treatment, its frequent drug dosing, and the adverse effects of anti-TB drugs. In this study, we have developed two nanocomposites (A and B) by intercalating the anti-TB drug isoniazid (INH) into Zn/Al-layered double hydroxides. The average size of the nanocomposites was found to bê164 nm. The efficacy of the Zn/Al-layered double hydroxides intercalated INH against Mycobacterium tuberculosis was increased by approximately three times more than free INH. The nanocomposites were also found to be active against Gram-positive and -negative bacteria. Compared to the free INH, the nanodelivery formulation was determined to be three times more biocompatible with human normal lung fibroblast MRC-5 cells and 3T3 fibroblast cells at a very high concentration of 50 µg/mL for up to 72 hours. The in vitro release of INH from the Zn/Al-layered double hydroxides was found to be sustained in human body-simulated buffer solutions of pH 4.8 and 7.4. This research is a step forward in making the TB chemotherapy patient friendly. PMID:27486322

From nicotinate-containing layered double hydroxides (LDHs) to NAD coenzyme-LDH nanocomposites - Syntheses and structural characterization by various spectroscopic methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Dudás, Csilla; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

2017-07-01

The syntheses of nicotinate anion- and NAD coenzyme-layered double hydroxide (LDH) composites were performed with the aim of having the organic component among the layers. In-house prepared CaAl-LDHs were the host materials. Intercalation was attempted by direct ion exchange or by the dehydration-rehydration method applying aqueous solvent mixtures (containing ethanol, propanol, acetone, N,N-dimethylformamide). For structural characterization, beside X-ray diffractometry, X-ray photoelectron and IR spectroscopies, transmission and scanning electron microscopies as well as energy-dispersive X-ray analysis were used. Molecular modelling served for the visualization of the arrangements of the intercalated ions among the layers of the LDH samples. Although not all the intercalation methods and solvent mixtures led to intercalated composite materials, successful ones could be identified. The combination of spectroscopic methods helped in proposing sensible spatial arrangements for the intercalated anions. The NAD-CaAl-LDH composite proved to be an active catalyst in the oxidation of hydroquinone to 1,4-bezoquinoe in the presence of H2O2.

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Daojin; Cai, Zhao; Bi, Yongmin

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Effects of redox-active interlayer anions on the oxygen evolution reactivity of NiFe-layered double hydroxide nanosheets

DOE PAGES

Zhou, Daojin; Cai, Zhao; Bi, Yongmin; ...

2018-02-02

Nickel-iron layered double hydroxide (NiFe-LDH) nanosheets have shown optimal oxygen evolution reaction (OER) performance; however, the role of the intercalated ions in the OER activity remains unclear. In this work, we show that the activity of the NiFe-LDHs can be tailored by the intercalated anions with different redox potentials. The intercalation of anions with low redox potential (high reducing ability), such as hypophosphites, leads to NiFe-LDHs with low OER overpotential of 240 mV and a small Tafel slope of 36.9 mV/dec, whereas NiFe-LDHs intercalated with anions of high redox potential (low reducing ability), such as fluorion, show a high overpotentialmore » of 370 mV and a Tafel slope of 80.8 mV/dec. The OER activity shows a surprising linear correlation with the standard redox potential. Density functional theory calculations and X-ray photoelectron spectroscopy analysis indicate that the intercalated anions alter the electronic structure of metal atoms which exposed at the surface. Anions with low standard redox potential and strong reducing ability transfer more electrons to the hydroxide layers. Finally, this increases the electron density of the surface metal sites and stabilizes their high-valence states, whose formation is known as the critical step prior to the OER process.« less

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

In situ oligomerization of 2-(thiophen-3-yl)acetate intercalated into Zn{sub 2}Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tronto, Jairo, E-mail: jairotronto@ufv.br; Pinto, Frederico G.; Costa, Liovando M. da

2015-01-15

A layered double hydroxide (LDH) with cation composition Zn{sub 2}Al was intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers. To achieve in situ polymerization and/or oligomerization of the intercalated monomers, soft thermal treatments were carried out, and subsequent hybrid LDH materials were analyzed by means of several characterization techniques using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), {sup 13}C CP–MAS nuclear magnetic resonance (NMR), electron spin resonance (EPR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and elemental analysis. PXRD analysis suggested that the intercalated monomers formed a bilayer. Thermalmore » treatment of the hybrid LDH assembly above 120 °C provokes partially the breakdown of the layered structure, generating the phase zincite. EPR results indicated that vicinal monomers (oligomerization) were bound to each other after hydrothermal or thermal treatment, leading to a polaron response characteristic of electron conductivity localized on a restricted number of thiophene-based monomer segments. Localized unpaired electrons exist in the material and interact with the {sup 27}Al nuclei of the LDH layers by superhyperfine coupling. These unpaired electrons also interact with the surface of ZnO (O{sup 2−} vacancies), formed during the thermal treatments. - Graphical abstract: We synthesized a layered double hydroxide (LDH) with cation composition Zn{sub 2}Al, intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers, by coprecipitation at constant pH. We thermally treated the material, to achieve in situ polymerization and/or oligomerization of the intercalated monomers. - Highlights: • A Zn{sub 2}Al–LDH was intercalated with 2-(thiophen-3-yl)acetate monomers. • To achieve in situ oligomerization of the monomers, thermal treatments were made. • Thermal treatment above 120 °C causes partially breakdown of the LDH structure. • ESR results indicated a polaron response characteristic of electron conductivity.« less

In Situ Formation of Decavanadate-Intercalated Layered Double Hydroxide Films on AA2024 and their Anti-Corrosive Properties when Combined with Hybrid Sol Gel Films

PubMed Central

Wu, Junsheng; Peng, Dongdong; He, Yuntao; Du, Xiaoqiong; Zhang, Zhan; Zhang, Bowei; Li, Xiaogang; Huang, Yizhong

2017-01-01

A layered double hydroxide (LDH) film was formed in situ on aluminum alloy 2024 through a urea hydrolysis method, and a decavanadate-intercalated LDH (LDH-V) film fabricated through the dip coating method. The microstructural and morphological characteristics were investigated by scanning electron microscopy (SEM). The corrosion-resistant performance was analyzed by electrochemical impedance spectroscopy (EIS), scanning electrochemical microscopy (SECM), and a salt-spray test (SST).The SEM results showed that a complete and defect-free surface was formed on the LDH-VS film. The anticorrosion results revealed that the LDH-VS film had better corrosion-resistant properties than the LDH-S film, especially long-term corrosion resistance. The mechanism of corrosion protection was proposed to consist of the self-healing effect of the decavanadate intercalation and the shielding effect of the sol-gel film. PMID:28772785

Methotrexate intercalated ZnAl-layered double hydroxide

NASA Astrophysics Data System (ADS)

Chakraborty, Manjusha; Dasgupta, Sudip; Soundrapandian, Chidambaram; Chakraborty, Jui; Ghosh, Swapankumar; Mitra, Manoj K.; Basu, Debabrata

2011-09-01

The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 Å in pristine LDH to 21.3 Å in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug molecule in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion.

Preparation of an anionic azo pigment-pillared layered double hydroxide and the thermo- and photostability of the resulting intercalated material

NASA Astrophysics Data System (ADS)

Guo, Shengchang; Li, Dianqing; Zhang, Weifeng; Pu, Min; Evans, David G.; Duan, Xue

2004-12-01

A large anionic pigment has been intercalated into a layered double hydroxide (LDH) host by ion-exchange of an Mg/Al LDH-nitrate precursor with a solution of C.I. Pigment Red 48:2 (the calcium salt of 4-((5-chloro-4-methyl-2-sulfophenyl)azo)-3-hydroxy-2-naphthalene-carboxylic acid), in ethane-1,2-diol. After intercalation of the pigment, the interlayer distance in the LDH increases from 0.86 to 1.72 nm. Infrared spectra and TG-DTA curves reveal the presence of a complex system of supramolecular host-guest interactions. The UV-visible diffuse reflectance spectra of C.I. Pigment Red 48:2 show marked changes after heating at 200 °C and above, whereas there are no significant changes in the spectra of the intercalated pigment after heating at temperatures up to 300 °C, showing that the thermostability is markedly enhanced by intercalation in the LDH host. The pigment-intercalated LDHs exhibits much higher photostability to UV light than the pristine pigment, in the case of both the pure solids and their composites with polypropylene, as shown by measurement of CIE 1976 L*a*b* color difference ( ΔE) values.

Synthesis and reversible hydration behavior of the thiosulfate intercalated layered double hydroxide of Zn and Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radha, S.; Milius, Wolfgang; Breu, Josef, E-mail: josef.breu@uni-bayreuth.de

2013-08-15

The thiosulfate-intercalated layered double hydroxide of Zn and Al undergoes reversible hydration with a variation in the relative humidity of the ambient. The hydrated and dehydrated phases, which represent the end members of the hydration cycle, both adopt the structure of the 3R{sub 1} polytype. In the intermediate range of relative humidity values (40–60%), the hydrated and dehydrated phases coexist. The end members of the hydration cycle adopt the structure of the same polytype, and vary only in their basal spacings. This points to the possibility that all the intermediate phases have a kinetic origin. - Graphical abstract: Basal spacingmore » evolution of the thiosulfate ion intercalated [Zn–Al] LDH during one complete hydration–dehydration cycle as a function of relative humidity. Display Omitted - Highlights: • Thiosulfate intercalated [Zn–Al] LDHs were synthesized by co-precipitation. • The LDH exhibits reversible hydration with variation in humidity. • Both the end members of the hydration cycle adopt the same polytype structure. • The interstratified intermediates observed are kinetic in origin.« less

Synthesis and characterization of Zn-Ti layered double hydroxide intercalated with cinnamic acid for cosmetic application

NASA Astrophysics Data System (ADS)

Li, Yong; Tang, Liping; Ma, Xinxu; Wang, Xinrui; Zhou, Wei; Bai, Dongsheng

2017-08-01

The use of sunscreen is recently growing and their efficacy and safety must be taken into account since they are applied on the skin frequently. In this work, an organic ultraviolet (UV) ray absorbent, cinnamic acid (CA) was intercalated into Zn-Ti layered double hydroxide (LDH) by anion-exchange reaction. ZnTi-CA-LDH, a new type of host-guest UV-blocking material has been synthesized. Detailed structural and surface morphology of ZnTi-CA-LDH were characterized by XRD, FT-IR, SEM and TEM. ZnTi-CA-LDH exhibits a superior UV blocking ability compared to pure CA and ZnTi-CO3-LDH. The thermal stability of the intercalated ZnTi-CA-LDH was investigated by TG-DTA, which showed that the thermostability of CA was markedly enhanced after intercalation into ZnTi-CO3-LDH. The EPR data showed greatly decreased photocatalytic activity compared to common inorganic UV blocking agents TiO2 and ZnO. Furthermore, the sample was formulated in a sunscreen cream to study the matrix protective effect towards UV rays.

Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferencz, Zs.; Szabados, M.; Varga, G.

2016-01-15

A mechanochemical method (grinding the components without added water – dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution – wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure wasmore » also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic–inorganic nanocomposites: LDHs intercalated with amino acid anions. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.« less

Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barahuie, Farahnaz; Hussein, Mohd Zobir, E-mail: mzobir@putra.upm.edu.my; Arulselvan, Palanisamy

A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the propertiesmore » of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro. - Highlights: • We intercalated chlorogenic into Zn/Al-layered double hydroxide by ion-exchange and coprecipitation methods. • The two methods gave nanocomposites with slightly different physico-chemical properties. • Chlorogenate-zinc aluminium layered double hydroxide nanohybrids have the potential to be used as a controlled release formulation. • The thermal stability of chlorogenic acid is markedly enhanced upon the intercalation process. • The inhibition of cancer cell growth is higher for nanohybrids than for free chlorogenic acid.« less

Synthesis, characterization, and controlled release anticorrosion behavior of benzoate intercalated Zn-Al layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yi; Zhang, Dun, E-mail: zhangdun@qdio.ac.cn

2011-11-15

Graphical abstract: The benzoate anion released from Zn-Al LDHs provides a more effective long-term protection against corrosion of Q235 carbon steel in 3.5% NaCl solution. Highlights: {yields} A benzoate anion corrosion inhibitor intercalated Zn-Al layered double hydroxides (LDHs) has been assembled by coprecipitation method. {yields} The kinetic simulation indicates that the ion-exchange one is responsible for the release process and the diffusion through particle is the rate limiting step. {yields} A significant reduction of the corrosion rate is observed when the LDH nanohybrid is present in the corrosive media. -- Abstract: Corrosion inhibitor-inorganic clay composite including benzoate anion intercalated Zn-Almore » layered double hydroxides (LDHs) are assembled by coprecipitation. Powder X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectrum analyses indicate that the benzoate anion is successfully intercalated into the LDH interlayer and the benzene planes are vertically bilayer-positioned as a quasi-guest ion-pair form in the gallery space. Kinetic simulation for the release data, XRD and FT-IR analyses of samples recovered from the release medium indicate that ion-exchange is responsible for the release process and diffusion through the particle is also indicated to be the rate-limiting step. The anticorrosion capabilities of LDHs loaded with corrosion inhibitor toward Q235 carbon steel are analyzed by polarization curve and electrochemical impedance spectroscopy methods. Significant reduction of corrosion rate is observed when the LDH nanohybrid is present in the corrosive medium. This hybrid material may potentially be applied as a nanocontainer in self-healing coatings.« less

Intercalation and structural aspects of macroRAFT agents into MgAl layered double hydroxides.

PubMed

Kostadinova, Dessislava; Cenacchi Pereira, Ana; Lansalot, Muriel; D'Agosto, Franck; Bourgeat-Lami, Elodie; Leroux, Fabrice; Taviot-Guého, Christine; Cadars, Sylvian; Prevot, Vanessa

2016-01-01

Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n -butyl acrylate (BA) with molar masses ranging from 2000 to 4200 g mol -1 synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, into LDH containing magnesium(II) and aluminium(III) intralayer cations and nitrates as counterions (MgAl-NO 3 LDH). At basic pH, the copolymer chains (macroRAFT agents) carry negative charges which allowed the establishment of electrostatic interactions with the LDH interlayer and their intercalation. The resulting hybrid macroRAFT/LDH materials displayed an expanded interlamellar domain compared to pristine MgAl-NO 3 LDH from 1.36 nm to 2.33 nm. Depending on the nature of the units involved into the macroRAFT copolymer (only AA or AA and BA), the intercalation led to monolayer or bilayer arrangements within the interlayer space. The macroRAFT intercalation and the molecular structure of the hybrid phases were further characterized by Fourier transform infrared (FTIR) and solid-state 13 C, 1 H and 27 Al nuclear magnetic resonance (NMR) spectroscopies to get a better description of the local structure.

Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

PubMed

Meng, Zilin; Li, Xiaowei; Lv, Fengzhu; Zhang, Qian; Chu, Paul K; Zhang, Yihe

2015-11-01

Aspirin or acetylsalicylic acid (AA), a non-steroidal anti-inflammatory drug, is intercalated into Zn-Al-layered double hydroxides (ZnAl-LDHs) by co-precipitation and reconstruction methods. The composition, structure, and morphology of the intercalated products as well as their release behavior are determined experimentally and theoretically by Material Studio 5.5. Experimental results disclose the strong interaction between the LDHs sheets and AA in the intercalated ZnAl-LDHs produced by co-precipitation and slow release of AA from the intercalated ZnAl-LDHs in both phosphate buffered saline (PBS) and borate buffered saline (BBS) solutions. The percentage of AA released from the ZnAl-LDHs prepared by both methods in PBS (96.87% and 98.12%) are much more than those in BBS (68.59% and 81.22%) implying that both H4BO4(-) and H2PO4(-) can exchange with AA in the ZnAl-LDHs. After AA is released to PBS, ZnAl-LDHs break into small pieces. The experimental results are explained theoretically based on the calculation of the bonding energy between the anions and LDHs sheets as well as the AlO bond length change in the LDHs sheets. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanochemical synthesis of dodecyl sulfate anion (DS-) intercalated Cu-Al layered double hydroxide

NASA Astrophysics Data System (ADS)

Qu, Jun; He, Xiaoman; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-12-01

Dodecyl sulfate anion (DS-) was successfully intercalated into the gallery space of Cu-Al layered double hydroxides (LDH) by a non-heating mechanochemical route, in which basic cupric carbonate (Cu2(OH)2CO3) and aluminum hydroxide (Al(OH)3) were first dry ground and then agitated in SDS solution under ambient environment. The organics modified Cu-Al LDH showed good adsorption ability toward 2,4-dichlorophenoxyacetic acid (2, 4-D). The prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), CHS elemental analysis and Scanning electron microscopy (SEM). The LDH precursor prepared by ball-milling could directly react with SDS molecules forming a pure phase of DS- pillared Cu-Al LDH, which was not observed with the LDH product through the ion-exchange of DS- at room temperature. The process introduced here may be applied to manufacture other types of organic modified composites for pollutants removal and other applications.

Cu2+ ions as a paramagnetic probe to study the surface chemical modification process of layered double hydroxides and hydroxide salts with nitrate and carboxylate anions.

PubMed

Arizaga, Gregorio Guadalupe Carbajal; Mangrich, Antonio Salvio; Wypych, Fernando

2008-04-01

A layered zinc hydroxide nitrate (Zn5(OH)8(NO3)2.2H2O) and a layered double hydroxide (Zn/Al-NO3) were synthesized by coprecipitation and doped with different amounts of Cu2+ (0.2, 1, and 10 mol%), as paramagnetic probe. Although the literature reports that the nitrate ion is free (with D3h symmetry) between the layers of these two structures, the FTIR spectra of two zinc hydroxide nitrate samples show the C2v symmetry for the nitrate ion, whereas the g ||/A || value in the EPR spectra of Cu2+ is high. This fact suggests bonding of some nitrate ions to the layers of the zinc hydroxide nitrate. The zinc hydroxide nitrate was used as matrix in the intercalation reaction with benzoate, o-chlorobenzoate, and o-iodobenzoate ions. FTIR spectra confirm the ionic exchange reaction and the EPR spectroscopy reveals bonding of the organic ions to the inorganic layers of the zinc hydroxide nitrate, while the layered double hydroxides show only exchange reactions.

An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

PubMed Central

Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

2015-01-01

In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

Anion-intercalated layered double hydroxides modified test strips for detection of heavy metal ions.

PubMed

Wang, Nan; Sun, Jianchao; Fan, Hai; Ai, Shiyun

2016-01-01

In this work, a novel approach for facile and rapid detection of heavy metal ions using anion-intercalated layered double hydroxides (LDHs) modified test strips is demonstrated. By intercalating Fe(CN)6(4-) or S(2-) anions into the interlayers of LDHs on the filter paper, various heavy metal ions can be easily detected based on the color change before and after reaction between the anions and the heavy metal ions. Upon the dropping of heavy metal ions solutions to the test strips, the colors of the test strips changed instantly, which can be easily observed by naked eyes. With the decrease of the concentration, the color depth changed obviously. The lowest detection concentration can be up to 1×10(-6) mol L(-1). Due to the easily intercalation of anions into the interlayer of the LDHs on test trips, this procedure provides a general method for the construction of LDHs modified test strips for detection of heavy metal ions. The stability of the prepared test strips is investigated. Furthermore, all the results were highly reproducible. The test strips may have potential applications in environmental monitoring fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Layered double hydroxide/polyethylene terephthalate nanocomposites. Influence of the intercalated LDH anion and the type of polymerization heating method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herrero, M.; Martinez-Gallegos, S.; Labajos, F.M.

2011-11-15

Conventional and microwave heating routes have been used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate had been previously intercalated in the LDH. PXRD and TEM were used to detect the degree of dispersion of the filler and the type of the polymeric composites obtained, and FTIR spectroscopy confirmed that the polymerization process had taken place. The thermal stability of these composites, as studied by thermogravimetric analysis, was enhanced when the microwave heating method was applied. Dodecyl sulphate wasmore » more effective than terephthalate to exfoliate the samples, which only occurred for the terephthalate ones under microwave irradiation. - Graphical abstract: Conventional and microwave heating routes were used to prepare PET-LDH (polyethylene terephthalate-layered double hydroxide) composites with 1-10 wt% LDH by in situ polymerization. To enhance the compatibility between PET and the LDH, terephthalate or dodecyl sulphate was previously intercalated into the LDH. The microwave process improves the dispersion and the thermal stability of nanocomposites due to the interaction of the microwave radiation and the dipolar properties of EG and the homogeneous heating. Highlights: > LDH-PET compatibility is enhanced by preintercalation of organic anions. > Dodecylsulphate performance is much better than that of terephthalate. > Microwave heating improves the thermal stability of the composites. > Microwave heating improves as well the dispersion of the inorganic phase.« less

Highly Efficient Iodine Capture by Layered Double Hydroxides Intercalated with Polysulfides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Shulan; Islam, Saiful M.; Shim, Yurina

2014-12-23

We demonstrate strong iodine (I-2) vapor adsorption using Mg/Al layered double hydroxide (MgAl-LDH) nanocomposites intercalated with polysulfide (S-x(2-)) groups (S-x-LDH, x = 2, 4, 6). The as-prepared LDH/polysulfide hybrid materials display highly efficient iodine capture resulting from the reducing property of the intercalated polysulfides. During adsorption, the I-2 molecules are reduced to I-3(-) anions by the intercalated [S-x](2-) groups that simultaneously are oxidized to form S8. In addition to the chemical adsorption, additional molecular I-2 is physically captured by the LDH composites. As a result of these parallel processes, and despite their very low BET surface areas, the iodine capturemore » capacities of S-2-LDH, S-4-LDH, and S-6-LDH are similar to 1.32, 1.52, and 1.43 g/g, respectively, with a maximum adsorption of 152% (wt %). Thermogravimetric and differential thermal analysis (TG-DTA), energy dispersive X-ray spectroscopy (EDS), and temperature-variable powder X-ray diffraction (XRD) measurements show the resulting I-3(-) ions that intercalated into the LDH gallery have high thermal stability (>= 350 degrees C). The excellent iodine adsorption performance combined with the facile preparation points to the S-x-LDH systems as potential superior materials for adsorption of radioactive iodine, a waste product of the nuclear power industry.« less

Synthesis and characterization of Mg-Al-layered double hydroxides intercalated with cubane-1,4-dicarboxylate anions.

PubMed

Rezvani, Zolfaghar; Arjomandi Rad, Farzad; Khodam, Fatemeh

2015-01-21

In the present work, Mg2Al-layered double hydroxide (LDH) intercalated with cubane-1,4-dicarboxylate anions was prepared from the reaction of solutions of Mg(ii) and Al(iii) nitrate salts with an alkaline solution of cubane-1,4-dicarboxylic acid by using the coprecipitation method. The successful preparation of a nanohybrid of cubane-1,4-dicarboxylate(cubane-dc) anions with LDH was confirmed by powder X-ray diffraction, FTIR spectroscopy and thermal gravimetric analysis (TGA). The increase in the basal spacing of LDHs from 8.67 Å to 13.40 Å shows that cubane-dc anions were successfully incorporated into the interlayer space. Thermogravimetric analyses confirm that the thermal stability of the intercalated cubane-dc anions is greater than that of the pure form before intercalation because of host-guest interactions involving hydrogen bonds. The interlayer structure, hydrogen bonding, and subsequent distension of LDH compounds containing cubane-dc anions were shown by molecular simulation. The RDF (radial distribution function), mean square displacement (MSD), and self-diffusion coefficient were calculated using the trajectory files on the basis of molecular dynamics (MD) simulations, and the results indicated that the cubane-dc anions were more stable when intercalated into the LDH layers. A good agreement was obtained between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings.

The effect of interlayer anion on the reactivity of Mg-Al layered double hydroxides: improving and extending the customization capacity of anionic clays.

PubMed

Rojas, Ricardo; Bruna, Felipe; de Pauli, Carlos P; Ulibarri, M Ángeles; Giacomelli, Carla E

2011-07-01

Layered double hydroxides (LDHs) reactivity and interfacial behavior are closely interconnected and control particle properties relevant to the wide range of these solids' applications. Despite their importance, their relationship has been hardly described. In this work, chloride and dodecylsulfate (DDS(-)) intercalated LDHs are studied combining experimental data (electrophoretic mobility and contact angle measurements, hydroxyl and organic compounds uptake) and a simple mathematical model that includes anion-binding and acid-base reactions. This approach evidences the anion effect on LDHs interfacial behavior, reflected in the opposite particle charge and the different surface hydrophobic/hydrophilic character. LDHs reactivity are also determined by the interlayer composition, as demonstrated by the cation uptake capability of the DDS(-) intercalated sample. Consequently, the interlayer anion modifies the LDHs interfacial properties and reactivity, which in turn extends the customization capacity of these solids. Copyright © 2011 Elsevier Inc. All rights reserved.

Reduction of biselenites into polyselenides in interlayer space of layered double hydroxides

NASA Astrophysics Data System (ADS)

Kim, Myeong Shin; Lee, Yongju; Park, Yong-Min; Cha, Ji-Hyun; Jung, Duk-Young

2018-06-01

A selenous acid (H2SeO3) precursor was intercalated as biselenite (HSeO3-) ions into the interlayer gallery of carbonated magnesium aluminum layered double hydroxide (MgAl-LDH) in aqueous solution. Reduction reaction of selenous ions by aqueous hydrazine solution produced polyselenide intercalated LDHs which were consecutively exchanged with iodide through redox reaction under iodine vapor. The polyselenide containing LDHs adsorbed iodine vapor spontaneously and triiodide was incorporated in the interlayer space followed by formation of selenium polycrystalline phase. Two dimensional framework of MgAl-LDH is strong enough to resist against the reducing power of hydrazine as well as oxidation condition of iodine. The SEM data demonstrated that the shapes of LDH polycrystalline have little changed after the above redox reactions. The polyselenide and iodide LDH products were analyzed by XRD, Infrared and Raman spectra which strongly suggested the horizontal arrangement of polyselenide and triiodide in gallery space of LDHs.

Intercalation of IR absorber into layered double hydroxides: Preparation, thermal stability and selective IR absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Haifeng; Tang, Pinggui; Feng, Yongjun, E-mail: yjfeng@mail.buct.edu.cn

2012-03-15

Highlights: Black-Right-Pointing-Pointer PMIDA anions were intercalated into Mg{sub 2}Al-NO{sub 3} LDH by anion-exchange method. Black-Right-Pointing-Pointer The prepared material has highly selective IR absorption property in 9-11 {mu}m. Black-Right-Pointing-Pointer The obtained material has practical applications as heat-retaining additive. -- Abstract: N-phosphonomethyl aminodiacetic acid (PMIDA) was intercalated into the interlayer spacing of layered double hydroxides (LDH) by an anion-exchange method. The intercalated LDHs were characterized by various techniques such as powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and simultaneous thermogravimetric and mass spectrometry (TG-MS) in details. The results show the formation of Mg{sub 2}Al-PMIDA LDH based on the expansion of d-spacingmore » from 0.89 nm to 1.22 nm and the disappearance of the characteristic IR absorption band at 1384 cm{sup -1} for NO{sub 3}{sup -} anions. The incorporation of Mg{sub 2}Al-PMIDA LDH into the low density polyethylene (LDPE) as an additive enhances the selectivity of IR absorption in the main wavelength region 9-11 {mu}m for radiant heat loss at night. Mg{sub 2}Al-PMIDA LDH as a heat-retaining additive has practical application in agricultural plastic films.« less

Multi-Anion Intercalated Layered Double Hydroxide Nanosheet-Assembled Hollow Nanoprisms with Improved Pseudocapacitive and Electrocatalytic Properties.

PubMed

Li, Zhengping; Han, Fangchun; Li, Cheng; Jiao, Xiuling; Chen, Dairong

2018-05-04

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one-step wet-chemical strategy for co-engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo-LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self-templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well-defined NiCo-LDH hollow nanoprisms (HNPs) with multi-anion intercalation. The unique hierarchical nanosheet-assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo-LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo-based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well-defined nanostructures for electrochemical applications and beyond. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structure refinement and chromate sorption characteristics of an Al-rich bayerite-based layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Britto, Sylvia, E-mail: sylviabritto11@gmail.com; Kamath, P. Vishnu

2014-07-01

“Imbibition” of Zn{sup 2+} ions into the cation vacancies of bayerite–Al(OH){sub 3} and NO{sub 3}{sup −} ions into the interlayer gallery yields an Al-rich layered double hydroxide with Al/Zn ratio ∼3. NO{sub 3}{sup −} ions are intercalated with their molecular planes inclined at an angle to the plane of the metal hydroxide slab and bonded to it by hydrogen bonds. Rietveld refinement of the structure shows that the monoclinic symmetry of the precursor bayerite is preserved in the product, showing that the imbibition is topochemical in nature. The nitrate ion is labile and is quantitatively replaced by CrO{sub 4}{sup 2−}more » ions from solution. The uptake of CrO{sub 4}{sup 2−} ions follows a Langmuir adsorption isotherm, thus showing that the hydroxide is a candidate material for green chemistry applications for the removal of CrO{sub 4}{sup 2−} ions from waste water. Rietveld refinement of the structure of the hydroxide after CrO{sub 4}{sup 2−} inclusion reveals that the CrO{sub 4}{sup 2−} ion is intercalated with one of its 2-fold axes parallel to the b-crystallographic axis of the crystal, also the principal 2 axis of the monoclinic cell. - Graphical abstract: The structure of the [Zn–Al4-nitrate] LDH viewed along the a-axis. - Highlights: • Synthesis of Al-rich layered double hydroxide with Al/Zn ratio ∼3. • Rietveld refinement indicates that the imbibition of Zn into Al(OH){sub 3} is topochemical in nature. • The uptake of CrO{sub 4}{sup 2−} ions follows a Langmuir adsorption isotherm.« less

Toxicity and Metabolism of Layered Double Hydroxide Intercalated with Levodopa in a Parkinson’s Disease Model

PubMed Central

Kura, Aminu Umar; Ain, Nooraini Mohd; Hussein, Mohd Zobir; Fakurazi, Sharida; Hussein-Al-Ali, Samer Hasan

2014-01-01

Layered hydroxide nanoparticles are generally biocompatible, and less toxic than most inorganic nanoparticles, making them an acceptable alternative drug delivery system. Due to growing concern over animal welfare and the expense of in vivo experiments both the public and the government are interested to find alternatives to animal testing. The toxicity potential of zinc aluminum layered hydroxide (ZAL) nanocomposite containing anti-Parkinsonian agent may be determined using a PC 12 cell model. ZAL nanocomposite demonstrated a decreased cytotoxic effect when compared to levodopa on PC12 cells with more than 80% cell viability at 100 μg/mL compared to less than 20% cell viability in a direct levodopa exposure. Neither levodopa-loaded nanocomposite nor the un-intercalated nanocomposite disturbed the cytoskeletal structure of the neurogenic cells at their IC50 concentration. Levodopa metabolite (HVA) released from the nanocomposite demonstrated the slow sustained and controlled release character of layered hydroxide nanoparticles unlike the burst uptake and release system shown with pure levodopa treatment. PMID:24722565

Tungstocobaltate-pillared layered double hydroxides: Preparation, characterization, magnetic and catalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei Xiaocui; Baicheng College of Higher Medicine, Baicheng 137000; Fu Youzhi

2008-06-15

A new polyoxometalate anion-pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange of a Mg-Al LDH precursor in nitrate form with the tungstocobaltate anions [CoW{sub 12}O{sub 40}]{sup 5-}. The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. It was confirmed that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without a change in the structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activitymore » for the oxidation of benzaldehyde by hydrogen peroxide. - Graphical abstract: A tungstocobaltate anion [CoW{sub 12}O{sub 40}]{sup 5-} pillared layered double hydroxide (LDH) was prepared by aqueous ion exchange with a Mg-Al LDH precursor in nitrate form, demonstrating that [CoW{sub 12}O{sub 40}]{sup 5-} was intercalated between the brucite-type layers of the LDHs without change in structure. Magnetic measurement shows the occurrence of antiferromagnetic interactions between the magnetic centers. The investigation of catalytic performance for this sample exhibits high activity for the oxidation of benzaldehyde by hydrogen peroxide.« less

Delamination-restacking behaviour of surfactant intercalated layered hydroxy double salts, M 3Zn 2(OH) 8(surf) 2ṡ2H 2O [M = Ni, Co and surf = dodecyl sulphate (DS), dodecyl benzene sulphonate (DBS)

NASA Astrophysics Data System (ADS)

Rajamathi, Jacqueline T.; Ravishankar, N.; Rajamathi, Michael

2005-02-01

Surfactant anion intercalated nickel-zinc and cobalt-zinc layered hydroxy double salts were prepared through a modified acetate hydrolysis route. These organo-inorganic hybrids delaminate readily in alcohols such as 1-butanol to give stable translucent colloids. The extent of delamination and the stability of the colloids obtained are comparable to what has been observed in the case of layered double hydroxides (LDHs). The original layered solid could be obtained either by evaporation of the colloid or precipitation by the addition of a polar solvent such as acetone.

Synthesis, characterization, and controlled release antibacterial behavior of antibiotic intercalated Mg–Al layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yi; Zhang, Dun, E-mail: zhangdun@qdio.ac.cn

Graphical abstract: The antibiotic anion released from Mg–Al LDHs provides a controlled release antibacterial activity against the growth of Micrococcus lysodeikticus in 3.5% NaCl solution. Highlights: ► Antibiotic anion intercalated LDHs were synthesized and characterized. ► The ion-exchange one is responsible for the release process. ► The diffusion through particle is the release rate limiting step. ► LDHs loaded with antibiotic anion have high antibacterial capabilities. -- Abstract: Antibiotic–inorganic clay composites including four antibiotic anions, namely, benzoate (BZ), succinate (SU), benzylpenicillin (BP), and ticarcillin (TC) anions, intercalated Mg–Al layered double hydroxides (LDHs) were synthesized via ion-exchange. Powder X-ray diffraction andmore » Fourier transform infrared spectrum analyses showed the successful intercalation of antibiotic anion into the LDH interlayer. BZ and BP anions were accommodated in the interlayer region as a bilayer, whereas SU and TC anions were intercalated in a monolayer arrangement. Kinetic simulation of the release data indicated that ion-exchange was responsible for the release process, and the diffusion through the particles was the rate-limiting step. The antibacterial capabilities of LDHs loaded with antibiotic anion toward Micrococcus lysodeikticus growth were analyzed using a turbidimetric method. Significant high inhibition rate was observed when LDH nanohybrid was introduced in 3.5% NaCl solution. Therefore, this hybrid material may be applied as nanocontainer in active antifouling coating for marine equipment.« less

Kinetics of intercalation of fluorescent probes in magnesium–aluminium layered double hydroxide within a multiscale reaction–diffusion framework

PubMed Central

Saliba, Daniel

2016-01-01

We report the synthesis of magnesium–aluminium layered double hydroxide (LDH) using a reaction–diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium–aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue ‘Multiscale modelling at the physics–chemistry–biology interface’. PMID:27698034

Kinetics of intercalation of fluorescent probes in magnesium-aluminium layered double hydroxide within a multiscale reaction-diffusion framework

NASA Astrophysics Data System (ADS)

Saliba, Daniel; Al-Ghoul, Mazen

2016-11-01

We report the synthesis of magnesium-aluminium layered double hydroxide (LDH) using a reaction-diffusion framework (RDF) that exploits the multiscale coupling of molecular diffusion with chemical reactions, nucleation and growth of crystals. In an RDF, the hydroxide anions are allowed to diffuse into an organic gel matrix containing the salt mixture needed for the precipitation of the LDH. The chemical structure and composition of the synthesized magnesium-aluminium LDHs are determined using powder X-ray diffraction (PXRD), thermo-gravimetric analysis, differential scanning calorimetry, solid-state nuclear magnetic resonance (SSNMR), Fourier transform infrared and energy dispersive X-ray spectroscopy. This novel technique also allows the investigation of the mechanism of intercalation of some fluorescent probes, such as the neutral three-dimensional rhodamine B (RhB) and the negatively charged two-dimensional 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), using in situ steady-state fluorescence spectroscopy. The incorporation of these organic dyes inside the interlayer region of the LDH is confirmed via fluorescence microscopy, solid-state lifetime, SSNMR and PXRD. The activation energies of intercalation of the corresponding molecules (RhB and HPTS) are computed and exhibit dependence on the geometry of the involved probe (two or three dimensions), the charge of the fluorescent molecule (anionic, cationic or neutral) and the cationic ratio of the corresponding LDH. This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'.

Interlayer interaction in Ca-Fe layered double hydroxides intercalated with nitrate and chloride species

NASA Astrophysics Data System (ADS)

Al-Jaberi, Muayad; Naille, Sébastien; Dossot, Manuel; Ruby, Christian

2015-12-01

Ca-Fe layered double hydroxide (LDH) intercalated with chloride and nitrate ions has been synthesized with varying CaII:FeIII molar ratios of the initial solution. Phase pure LDH is observed with CaII:FeIII molar ratio of 2:1 and a mixture of LDH and Ca(OH)2 is formed for CaII:FeIII molar ratios higher than 2:1. Vibrational spectroscopies (Raman and IR) were used successfully to understand the interaction between the cationic and anionic sheets. The Raman bands positions at lower frequencies (150-600 cm-1) are intimately correlated to the nature of the divalent and trivalent ions but also to the nature of the anions. Indeed, a shift of ˜9 cm-1 is observed for the Raman double bands situated in the 300-400 cm-1 region when comparing Raman spectra of CaFe-LDH containing either nitrate or chloride ions. Two types of nitrate environments are observed namely free (non-hydrogen bonded) nitrate and nitrate hydrogen bonded to the interlayer water or to the 'brucite-like' hydroxyl surface. Multiple types of water structure are observed and would result from different hydrogen bond structures. Water bending modes are identified at 1645 cm-1 greater than the one observed for LDH intercalated with chloride anions (1618 cm-1), indicating that the water is strongly hydrogen bonded to the nitrate anions.

CdS-pillared CoAl-layered double hydroxide nanosheets with superior photocatalytic activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Yanqiang; Lin, Bizhou, E-mail: bzlin@hqu.edu.cn; Jia, Fangcao

Graphical abstract: - Highlights: • CdS nanocrystals were intercalated into CoAl-LDH interlayer. • The nanohybrid display superior visible-light photocatalytic activity. • A photoexcitation model for the pillared heterostructured system was proposed. - Abstract: A new nanohybrid was synthesized by mixing the positively charged 2D nanosheets of CoAl-layered double hydroxide (CoAl-LDH) and the negatively charged CdS nanosol suspensions. It was revealed that the CdS nanoparticles were intercalated into the interlayer region of CoAl-LDH with a spacing of 2.62 nm. The obtained nanohybrid exhibited a mesoporous texture with an expanded specific surface area of 62 m{sup 2} g{sup −1} and a superiormore » photocatalytic activity in the degradation of acid red with a reaction constant of 1.26 × 10{sup −2} min{sup −1} under visible-light radiation, which is more than 2 times those of his parents CoAl-LDH and CdS.« less

High-temperature chemical and microstructural transformations of an organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Hui; Guo Shaohuan; Zou Kang

The thermal evolution of a crystalline organic-inorganic nanohybrid captopril intercalated Mg-Al layered double hydroxide (LDH) [Mg{sub 0.68}Al{sub 0.32}(OH){sub 2}] (C{sub 9}H{sub 13}NO{sub 3}S){sub 0.130}(CO{sub 3}){sub 0.030}.0.53H{sub 2}O obtained by coprecipitation method is studied based upon in situ high-temperature X-ray diffraction, in situ infrared and thermogravimetric analysis coupled with mass spectroscopy analysis. The results reveal that a metastable quasi-interstratified layered nanohybrid involving carbonate-LDH and reoriented less ordered captopril-LDH was firstly observed as captopril-LDH heat-treated between 140 and 230 deg. C. The major decomposition/combustion of interlayer organics occur between 270 and 550 deg. C. A schematic model on chemical and microstructural evolutionmore » of this particular drug-inorganic nanohybrid upon heating in air atmosphere is proposed.« less

Sol-gel synthesis and characterization of hybrid inorganic-organic Tb(III)-terephthalate containing layered double hydroxides

NASA Astrophysics Data System (ADS)

Smalenskaite, A.; Salak, A. N.; Ferreira, M. G. S.; Skaudzius, R.; Kareiva, A.

2018-06-01

Mg3/Al1 and Mg3Al1-xTbx layered double hydroxides (LDHs) intercalated with terephthalate anion were synthesized using sol-gel method. The obtained materials were characterized by X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy, fluorescence spectroscopy (FLS) and scanning electron microscopy (SEM). The Tb3+ substitution effects in the Mg3Al1-xTbx LDHs were investigated by changing the Tb3+ concentration in the cation layers. The study indicates that the organic guest-terephthalate in the interlayer spacing of the LDH host influences the luminescence of the hybrid inorganic-organic materials.

Anionic surfactant enhanced phosphate desorption from Mg/Al-layered double hydroxides by micelle formation.

PubMed

Shimamura, Akihiro; Jones, Mark I; Metson, James B

2013-12-01

Desorption of interlayer hydrogen phosphate (HPO4) from hydrogen phosphate intercalated Mg/Al-layered double hydroxide (LDH-HPO4) by anion exchange with surfactant anions has been investigated under controlled conditions. Three types of surfactant, Dodecylbenzenesulphonate (DBS), Dodecylsulphate (DS) and 1-Octanesulphonate (OS), anions were used for intercalation experiments over a range of concentrations, and for all solutions, it was shown that the desorption of hydrogen phosphate is enhanced at concentrations close to the critical micelle concentration (CMC). Intercalation of the surfactant anions into LDH-HPO4 was confirmed by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning electron microscopy (SEM). More than 90% removal of the hydrogen phosphate was achieved at CMC. Repeat adsorption tests to investigate recyclability showed that desorption with 0.005 M DBS improved subsequent phosphate re-adsorption, allowing around 90% of the original adsorption over three cycles. This is much higher than when desorption was conducted using either Na2CO3 or NaCl-NaOH solutions, even at much higher concentrations. This study suggests potential economic and environmental advantages in using these surfactants in improving the cycling performance of LDH materials as absorbents for clean-up of water systems. Copyright © 2013 Elsevier Inc. All rights reserved.

Synthesis of protocatechuic acid-zinc/aluminium-layered double hydroxide nanocomposite as an anticancer nanodelivery system

NASA Astrophysics Data System (ADS)

Barahuie, Farahnaz; Hussein, Mohd Zobir; Gani, Shafinaz Abd; Fakurazi, Sharida; Zainal, Zulkarnain

2015-01-01

Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al-layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al-NO3-LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formation of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment.

Platelets to rings: Influence of sodium dodecyl sulfate on Zn-Al layered double hydroxide morphology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yilmaz, Ceren; Unal, Ugur; Koc University, Chemistry Department, Rumelifeneri yolu, Sariyer 34450, Istanbul

2012-03-15

In the current study, influence of sodium dodecyl sulfate (SDS) on the crystallization of Zn-Al layered double hydroxide (LDH) was investigated. Depending on the SDS concentration coral-like and for the first time ring-like morphologies were obtained in a urea-hydrolysis method. It was revealed that the surfactant level in the starting solution plays an important role in the morphology. Concentration of surfactant equal to or above the anion exchange capacity of the LDH is influential in creating different morphologies. Another important parameter was the critical micelle concentration (CMC) of the surfactant. Surfactant concentrations well above CMC value resulted in ring-like structures.more » The crystallization mechanism was discussed. - Graphical abstract: Dependence of ZnAl LDH Morphology on SDS concentration. Highlights: Black-Right-Pointing-Pointer In-situ intercalation of SDS in ZnAl LDH was achieved via urea hydrolysis method. Black-Right-Pointing-Pointer Morphology of ZnAl LDH intercalated with SDS depended on the SDS concentration. Black-Right-Pointing-Pointer Ring like morphology for SDS intercalated ZnAl LDH was obtained for the first time. Black-Right-Pointing-Pointer Growth mechanism was discussed. Black-Right-Pointing-Pointer Template assisted growth of ZnAl LDH was proposed.« less

Synthesis and characterization of protocatechuic acid-loaded gadolinium-layered double hydroxide and gold nanocomposite for theranostic application

NASA Astrophysics Data System (ADS)

Usman, Muhammad Sani; Hussein, Mohd Zobir; Kura, Aminu Umar; Fakurazi, Sharida; Masarudin, Mas Jaffri; Saad, Fathinul Fikri Ahmad

2018-03-01

A theranostic nanocomposite was developed using anticancer agent, protocatechuic acid (PA) and magnetic resonance imaging (MRI) contrast agent gadolinium nitrate (Gd) for simultaneous delivery using layered double hydroxide (LDH) as the delivery agent. Gold nanoparticles (AuNPs) were adsorbed on the surface of the LDH, which served as a complementary contrast agent. Based on the concept of supramolecular chemistry (SPC) and multimodal delivery system (MDS), the PA and Gd guests were first intercalated into the LDH host and subsequently AuNPs were surface adsorbed as the third guest. The nanohybrid developed was named MAPGAu. The MAPGAu was exposed to various characterizations at different stages of synthesis, starting with XRD analysis, which was used to confirm the intercalation episode and surface adsorption of the guest molecules. Consequently, FESEM, Hi-TEM, XRD, ICP-OES, CHNS, FTIR and UV-Vis analyses were done on the nanohybrids. The result of XRD analysis indicated successful intercalation of the Gd and PA as well the adsorption of AuNPs. The UV-Vis release study showed 90% of the intercalated drug was released at pH 4.8, which is the pH of the cancer cells. The FESEM and TEM micrographs obtained equally confirmed the formation of MAGPAu nanocomposite, with AuNPs conspicuously deposited on the LDH surface. The cytotoxicity study of the nanohybrid also showed insignificant toxicity to normal cell lines and significant toxicity to cancer cell lines. The developed MAGPAu nanocomposite has shown prospects for future theranostic cancer treatment.

Functional intercalated nanocomposites with chitosan-glutathione-glycylsarcosine and layered double hydroxides for topical ocular drug delivery.

PubMed

Xu, Tingting; Xu, Xiaoyue; Gu, Yan; Fang, Lei; Cao, Feng

2018-01-01

To enhance ocular bioavailability, the traditional strategies have focused on prolonging precorneal retention and improving corneal permeability by nano-carriers with positive charge, thiolated polymer, absorption enhancer and so on. Glycylsarcosine (GS) as an active target ligand of the peptide tranpsporter-1 (PepT-1), could specific interact with the PepT-1 on the cornea and guide the nanoparticles to the treating site. The objective of the study was to explore the active targeting intercalated nanocomposites based on chitosan-glutathione-glycylsarcosine (CG-GS) and layered double hydroxides (LDH) as novel carriers for the treatment of mid-posterior diseases. CG-GS-LDH intercalated nanocomposites were prepared by the coprecipitation hydrothermal method. In vivo precorneal retention study, ex vivo fluorescence images, in vivo experiment for distribution and irritation were studied in rabbits. The cytotoxicity and cellular uptake were studied in human corneal epithelial primary cells (HCEpiC). CG-GS-LDH nanocomposites were prepared successfully and characterized by FTIR and XRD. Experiments with rabbits showed longer precorneal retention and higher distribution of fluorescence probe/model drug. In vitro cytological study, CG-GS-LDH nanocomposites exhibited enhanced cellular uptake compared to pure drug solution. Furthermore, the investigation of cellular uptake mechanisms demonstrated that both the active transport by PepT-1 and clathrin-mediated endocytosis were involved in the internalization of CG-GS-LDH intercalated nanocomposites. An ocular irritation study and a cytotoxicity test indicated that these nanocomposites produced no significant irritant effects. The active targeting intercalated nanocomposites could have great potential for topical ocular drug delivery due to the capacity for prolonging the retention on the ocular surface, enhancing the drug permeability through the cornea, and efficiently delivering the drug to the targeted site.

Functional intercalated nanocomposites with chitosan-glutathione-glycylsarcosine and layered double hydroxides for topical ocular drug delivery

PubMed Central

Gu, Yan

2018-01-01

Background To enhance ocular bioavailability, the traditional strategies have focused on prolonging precorneal retention and improving corneal permeability by nano-carriers with positive charge, thiolated polymer, absorption enhancer and so on. Glycylsarcosine (GS) as an active target ligand of the peptide tranpsporter-1 (PepT-1), could specific interact with the PepT-1 on the cornea and guide the nanoparticles to the treating site. Purpose The objective of the study was to explore the active targeting intercalated nanocomposites based on chitosan-glutathione-glycylsarcosine (CG-GS) and layered double hydroxides (LDH) as novel carriers for the treatment of mid-posterior diseases. Materials and methods CG-GS-LDH intercalated nanocomposites were prepared by the coprecipitation hydrothermal method. In vivo precorneal retention study, ex vivo fluorescence images, in vivo experiment for distribution and irritation were studied in rabbits. The cytotoxicity and cellular uptake were studied in human corneal epithelial primary cells (HCEpiC). Results CG-GS-LDH nanocomposites were prepared successfully and characterized by FTIR and XRD. Experiments with rabbits showed longer precorneal retention and higher distribution of fluorescence probe/model drug. In vitro cytological study, CG-GS-LDH nanocomposites exhibited enhanced cellular uptake compared to pure drug solution. Furthermore, the investigation of cellular uptake mechanisms demonstrated that both the active transport by PepT-1 and clathrin-mediated endocytosis were involved in the internalization of CG-GS-LDH intercalated nanocomposites. An ocular irritation study and a cytotoxicity test indicated that these nanocomposites produced no significant irritant effects. Conclusions The active targeting intercalated nanocomposites could have great potential for topical ocular drug delivery due to the capacity for prolonging the retention on the ocular surface, enhancing the drug permeability through the cornea, and efficiently delivering the drug to the targeted site. PMID:29491707

A novel method to delaminate nitrate-intercalated MgAl layered double hydroxides in water and application in heavy metals removal from waste water.

PubMed

Rahman, Mir Tamzid; Kameda, Tomohito; Kumagai, Shogo; Yoshioka, Toshiaki

2018-07-01

Nitrate-intercalated MgAl layered double hydroxide (LDH) was successfully delaminated in water by a facile and effective method upon reflux at 120 °C for 24 h followed by sonication at 40 °C for 5 h. This process is environmentally friendly since water is the only solvent used. The delaminated nanosheets were characterized by microscopic, spectroscopic, and particle size analyses. The delamination process successfully produced octahedron-shaped single-layer nanosheets 50-150 nm in size. X-ray photoelectron spectroscopy (XPS) data confirmed that the surface elements and their chemical status are consistent with the basic layer of MgAl LDH. The delaminated nanosheets displayed higher adsorption capacity for removing heavy metals from waste water than the original powdered LDH. After treating the waste water, a sharp and intense peak in the X-ray powder diffraction (XRD) pattern of the precipitate confirms the restacking of the LDH nanosheets. Copyright © 2018 Elsevier Ltd. All rights reserved.

Physical and Chemical Interactions between Mg:Al Layered Double Hydroxide and Hexacyanoferrate

NASA Astrophysics Data System (ADS)

Boclair, Joseph W.; Braterman, Paul S.; Brister, Brian D.; Wang, Zhiming; Yarberry, Faith

2001-11-01

The physical and chemical interactions of ferrocyanide (potassium and ammonium salts) and ferricyanide (potassium salt) with Mg:Al layered double hydroxides (LDH) (having Mg:Al ratios of 2 and 3) are investigated using powder XRD and FTIR spectroscopy. Physically, the potassium ferricyanide is shown to intercalate with a small local field deformation similar to that seen for hexacyanocobaltate (III) in similar materials. Chemically, the reduction of ferricyanide to ferrocyanide upon intercalation is confirmed. Physical interactions of ferrocyanide with 3:1 LDH are shown spectroscopically to include the possible generation of anions in differing environments. Chemically, ferrocyanide is shown to generate cubic ferrocyanides (of the type M2MgFe(CN)6, where M=K+ or NH+4) under conditions where free Mg2+ is likely present in solution, namely, solutions with a pH lower than ∼7.5. It is shown that the reported 2112-cm-1 band found in some chemically altered LDH ferrocyanide is indeed due to interlayer ferricyanide, but that the 2080 cm-1 band is due to the cubic material.

Synthesising methods of layered double hydroxides and its use in the fabrication of dye Sensitised solar cell (DSSC): A short review

NASA Astrophysics Data System (ADS)

George, Giphin; Saravanakumar, M. P.

2017-11-01

The layered double hydroxides (LDH) which are anionic clay substances comprising of stacked cationic layers and interlayer anions. The cationic sheets contain octahedral structure consisting the divalent and trivalent ions in the center and hydroxyl bunches in the corners, gathered by three bonding with the neighbouring octahedra on every side of the layer. The ratio between the quantity of cations and OH- ions is 2:1, so a positive charge shows up on the layer because of the presence of trivalent cations. The interlayer space gives the compensation anions and water molecules, assuring a balanced out layered structure. The LDH materials were successfully synthesised from magnesium, aluminium, zinc and chromium chloride salts utilizing the co-precipitation technique. A Zn-Al LDH was researched as a potential sorbent material. This article reviews the recent advances in the preparation and intercalation of layered double hydroxides and its application in the fabrication of Dye Sensitized Solar Cell (DSSC).

Composition driven monolayer to bilayer transformation in a surfactant intercalated Mg-Al layered double hydroxide.

PubMed

Naik, Vikrant V; Chalasani, Rajesh; Vasudevan, S

2011-03-15

The structure and organization of dodecyl sulfate (DDS) surfactant chains intercalated in an Mg-Al layered double hydroxide (LDH), Mg(1-x)Alx(OH)2, with differing Al/Mg ratios has been investigated. The Mg-Al LDHs can be prepared over a range of compositions with x varying from 0.167 to 0.37 and therefore provides a simple system to study how the organization of the alkyl chains of the intercalated DDS anions change with packing density; the Al/Mg ratio or x providing a convenient handle to do so. Powder X-ray diffraction measurements showed that at high packing densities (x ≥ 0.3) the alkyl chains of the intercalated dodecyl sulfate ions are anchored on opposing LDH sheets and arranged as bilayers with an interlayer spacing of ∼27 Å. At lower packing densities (x < 0.2) the surfactant chains form a monolayer with the alkyl chains oriented flat in the galleries with an interlayer spacing of ∼8 Å. For the in between compositions, 0.2 ≤ x < 0.3, the material is biphasic. MD simulations were performed to understand how the anchoring density of the intercalated surfactant chains in the Mg-Al LDH-DDS affects the organization of the chains and the interlayer spacing. The simulations are able to reproduce the composition driven monolayer to bilayer transformation in the arrangement of the intercalated surfactant chains and in addition provide insights into the factors that decide the arrangement of the surfactant chains in the two situations. In the bilayer arrangement, it is the dispersive van der Waals interactions between chains in opposing layers of the anchored bilayer that is responsible for the cohesive energy of the solid whereas at lower packing densities, where a monolayer arrangement is favored, Coulomb interactions between the positively charged Mg-Al LDH sheets and the negatively charged headgroup of the DDS anion dominate.

Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manohara, G.V.; Vishnu Kamath, P., E-mail: vishnukamath8@hotmail.com; Milius, Wolfgang

2012-12-15

Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueousmore » exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.« less

Reduction in the size of layered double hydroxide nanoparticles enhances the efficiency of siRNA delivery.

PubMed

Chen, Min; Cooper, Helen M; Zhou, Ji Zhi; Bartlett, Perry F; Xu, Zhi Ping

2013-01-15

Small interfering RNAs (siRNAs) are a potentially powerful new class of pharmaceutical drugs for many disease. However, the delivery of unprotected siRNAs is ineffective due to their susceptibility to degradation by ubiquitous nucleases under physiological conditions. Layered double hydroxide nanoparticles (LDHs) have been found to be efficient carriers of anionic drugs and nucleic acids. Our previous research has shown that LDHs (with the Z-average particle size of approximately 110 nm) can mediate siRNA delivery in mammalian cells, resulting in gene silencing. However, short double-stranded nucleic acids are mostly adsorbed onto the external surface and not well protected by LDHs. In order to enhance the intercalation of siRNA into the LDH interlayer and the efficiency of subsequent siRNA delivery, we prepared smaller LDHs (with the Z-average particle size of approximately 45 nm) with an engineered non-aqueous method. We demonstrate here that dsDNA/siRNA is more effectively intercalated into these small LDH nanoparticles, more dsDNA/siRNA is transfected into HEK 293T cells, and more efficient silencing of the target gene is achieved using smaller LDHs. Thus, smaller LDH particles have greater potential as a delivery system for the application of RNA interference. Copyright © 2012 Elsevier Inc. All rights reserved.

Synthesis and characterization of Cd Cr and Zn Cd Cr layered double hydroxides intercalated with dodecyl sulfate

NASA Astrophysics Data System (ADS)

Guo, Ying; Zhang, He; Zhao, Lan; Li, Guo-Dong; Chen, Jie-Sheng; Xu, Lin

2005-06-01

Cd-Cr and Zn-Cd-Cr layered double hydroxides (CdCr-LDH and ZnCdCr-LDH) containing alkyl sulfate as the interlamellar anion have been prepared through a coprecipitation technique. The resulting compounds were characterized using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Magnetic property measurements indicate that antiferromagnetic interactions occur between the chromium ions in the two compounds at low temperatures. The introduction of zinc influences the ligand field of Cr III and the Cr III-Cr III interactions in the LDH compound. It is found that both CdCr-LDH and ZnCdCr-LDH can be delaminated by dispersion in formamide, leading to translucent and stable colloidal solutions.

A solution blending route to ethylene propylene diene terpolymer/layered double hydroxide nanocomposites

PubMed Central

Acharya, H; Bhowmick, Anil K

2007-01-01

Ethylene propylene diene terpolymer (EPDM)/MgAl layered double hydroxide (LDH) nanocomposites have been synthesized by solution intercalation using organically modified LDH (DS-LDH). The molecular level dispersion of LDH nanolayers has been verified by the disappearance of basal XRD peak of DS-LDH in the composites. The internal structures, of the nanocomposite with the dispersion nature of LDH particles in EPDM matrix have been studied by TEM and AFM. Thermogravimetric analysis (TGA) shows thermal stability of nanocomposites improved by ≈40 °C when 10% weight loss was selected as point of comparison. The degradation for pure EPDM is faster above 380 °C while in case of its nanocomposites, it is much slower.

Synthesis and Properties of a Clean and Sustainable Deicing Additive for Asphalt Mixture

PubMed Central

Peng, Chao; Yu, Jianying; Zhao, Zhijie; Dai, Jing; Fu, Jingyi; Zhao, Meiling; Wang, Wei

2015-01-01

A clean and sustainable deicing additive was prepared via the adsorption of acetate anions (Ac-) by magnesium (Mg) and aluminum (Al) calcined layered double hydroxide (Mg/Al-CLDH). Fourier transform infrared spectroscopy spectrums proved that Ac- had intercalated into LDH structure. X-ray diffraction patterns, scanning electron microscopy and transmission electron microscopy images showed that the intercalation spacing and platelet thickness of Mg and Al layered double hydroxide containing Ac- anions (Mg/Al-Ac- LDH) had been enlarged due to substitution of divalent CO3 2- anions by a larger quantity of monovalent Ac– anions. Differential scanning calorimetry tests testified that the insoluble Mg2/Al-Ac- LDH evidently decreased the freeze point (FP) of water to -10.68°C. X-ray photoelectron spectroscopy analyses confirmed that the Ac- were strongly confined by the metal layers of LDHs. FP test of asphalt mixtures confirmed that Mg/Al-Ac- LDHs reduced FP to -5.5°C. Immersion test results indicated that Mg/Al-Ac- LDH had a good deicing durability and Ac- did not released from asphalt mixture. Snow melting observation was conducted further testified that Mg/Al-Ac- LDH melted snow or ice sustainably. PMID:25625279

Synthesis and properties of a clean and sustainable deicing additive for asphalt mixture.

PubMed

Peng, Chao; Yu, Jianying; Zhao, Zhijie; Dai, Jing; Fu, Jingyi; Zhao, Meiling; Wang, Wei

2015-01-01

A clean and sustainable deicing additive was prepared via the adsorption of acetate anions (Ac-) by magnesium (Mg) and aluminum (Al) calcined layered double hydroxide (Mg/Al-CLDH). Fourier transform infrared spectroscopy spectrums proved that Ac- had intercalated into LDH structure. X-ray diffraction patterns, scanning electron microscopy and transmission electron microscopy images showed that the intercalation spacing and platelet thickness of Mg and Al layered double hydroxide containing Ac- anions (Mg/Al-Ac- LDH) had been enlarged due to substitution of divalent CO32- anions by a larger quantity of monovalent Ac- anions. Differential scanning calorimetry tests testified that the insoluble Mg2/Al-Ac- LDH evidently decreased the freeze point (FP) of water to -10.68°C. X-ray photoelectron spectroscopy analyses confirmed that the Ac- were strongly confined by the metal layers of LDHs. FP test of asphalt mixtures confirmed that Mg/Al-Ac- LDHs reduced FP to -5.5°C. Immersion test results indicated that Mg/Al-Ac- LDH had a good deicing durability and Ac- did not released from asphalt mixture. Snow melting observation was conducted further testified that Mg/Al-Ac- LDH melted snow or ice sustainably.

Nanocomposites coated with xyloglucan for drug delivery: In vitro studies.

PubMed

Ribeiro, C; Arizaga, G G C; Wypych, F; Sierakowski, M-R

2009-02-09

Enalaprilate (Enal), an active pharmaceutical component, was intercalated into a layered double hydroxide (Mg/Al-LDH) by an ion exchange reaction. The use of a layered double hydroxide (LDH) to release active drugs is limited by the low pH of the stomach (pH approximately 1.2), in whose condition it is readily dissolved. To overcome this limitation, xyloglucan (XG) extracted from Hymenaea courbaril (jatobá) seeds, Brazilian species, was used to protect the LDH and allow the drug to pass through the gastrointestinal tract. All the materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, elemental analyses, transmission electronic microscopy, thermal analyses, and a kinetic study of the in vitro release was monitored by ultraviolet spectroscopy. The resulting hybrid system containing HDL-Enal-XG(3) slowly released the Enal. In an 8-h of test, the system protected 40% (w/v) of the drug. The kinetic profile showed that the drug release was a co-effect behavior, involving dissolution of inorganic material and ion exchange between the intercalated anions in the lamella and those of phosphate in the buffer solution. The nanocomposite coated protection with XG was therefore efficient in obtaining a slow release of Enal.

Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Jun, E-mail: zhqw1888@sohu.co; College of Chemical Engineering, Harbin Institute of Technology, Harbin 150001; Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, 150001

2010-11-15

We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs havingmore » different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted« less

Accessing the biocompatibility of layered double hydroxide by intramuscular implantation: histological and microcirculation evaluation

PubMed Central

Cunha, Vanessa Roberta Rodrigues; de Souza, Rodrigo Barbosa; da Fonseca Martins, Ana Maria Cristina Rebello Pinto; Koh, Ivan Hong Jun; Constantino, Vera Regina Leopoldo

2016-01-01

Biocompatibility of layered double hydroxides (LDHs), also known as hydrotalcite-like materials or double metal hydroxides, was investigated by in vivo assays via intramuscular tablets implantation in rat abdominal wall. The tablets were composed by chloride ions intercalated into LDH of magnesium/aluminum (Mg2Al-Cl) and zinc/aluminum (Zn2Al-Cl). The antigenicity and tissue integration capacity of LDHs were assessed histologically after 7 and 28 days post-implantation. No fibrous capsule nearby the LDH was noticed for both materials as well any sign of inflammatory reactions. Sidestream Dark Field imaging, used to monitor in real time the microcirculation in tissues, revealed overall integrity of the microcirculatory network neighboring the tablets, with no blood flow obstruction, bleeding and/or increasing of leukocyte endothelial adhesion. After 28 days Mg2Al-Cl promoted multiple collagen invaginations (mostly collagen type-I) among its fragments while Zn2Al-Cl induced predominantly collagen type–III. This work supports previous results in the literature about LDHs compatibility with living matter, endorsing them as functional materials for biomedical applications. PMID:27480483

Accessing the biocompatibility of layered double hydroxide by intramuscular implantation: histological and microcirculation evaluation.

PubMed

Cunha, Vanessa Roberta Rodrigues; de Souza, Rodrigo Barbosa; da Fonseca Martins, Ana Maria Cristina Rebello Pinto; Koh, Ivan Hong Jun; Constantino, Vera Regina Leopoldo

2016-08-02

Biocompatibility of layered double hydroxides (LDHs), also known as hydrotalcite-like materials or double metal hydroxides, was investigated by in vivo assays via intramuscular tablets implantation in rat abdominal wall. The tablets were composed by chloride ions intercalated into LDH of magnesium/aluminum (Mg2Al-Cl) and zinc/aluminum (Zn2Al-Cl). The antigenicity and tissue integration capacity of LDHs were assessed histologically after 7 and 28 days post-implantation. No fibrous capsule nearby the LDH was noticed for both materials as well any sign of inflammatory reactions. Sidestream Dark Field imaging, used to monitor in real time the microcirculation in tissues, revealed overall integrity of the microcirculatory network neighboring the tablets, with no blood flow obstruction, bleeding and/or increasing of leukocyte endothelial adhesion. After 28 days Mg2Al-Cl promoted multiple collagen invaginations (mostly collagen type-I) among its fragments while Zn2Al-Cl induced predominantly collagen type-III. This work supports previous results in the literature about LDHs compatibility with living matter, endorsing them as functional materials for biomedical applications.

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Enhancement of the coercivity in Co-Ni layered double hydroxides by increasing basal spacing.

PubMed

Zhang, Cuijuan; Tsuboi, Tomoya; Namba, Hiroaki; Einaga, Yasuaki; Yamamoto, Takashi

2016-09-14

The magnetic properties of layered double hydroxides (LDH) containing transition metal ions can still develop, compared with layered metal hydroxide salts which exhibit structure-dependent magnetism. In this article, we report the preparation of a hybrid magnet composed of Co-Ni LDH and n-alkylsulfonate anions (Co-Ni-CnSO3 LDH). As Co-Ni LDH is anion-exchangeable, we can systematically control the interlayer spacing by intercalating n-alkylsulfonates with different carbon numbers. The magnetic properties were examined with temperature- and field-dependent magnetization measurements. As a result, we have revealed that the coercive field depends on the basal spacing. It is suggested that increasing the basal spacing varies the competition between the in-plane superexchange interactions and long-range out-of-plane dipolar interactions. Moreover, a jump in the coercive field at around 20 Å of the basal spacing is assumed to be the modification of the magnetic ordering in Co-Ni-CnSO3 LDH.

Rare earth and zinc layered hydroxide salts intercalated with the 2-aminobenzoate anion as organic luminescent sensitizer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cursino, Ana Cristina Trindade, E-mail: anacursino@ufpr.br; Rives, Vicente, E-mail: vrives@usal.es; Arizaga, Gregorio Guadalupe Carbajal, E-mail: gregoriocarbajal@yahoo.com.mx

2015-10-15

Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The UV absorption ability was improved after intercalation/grafting in relation to that shown by the parent material. - Highlights: • Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide were synthesized. • Intercalated nitrate anions were exchanged by 2-aminobenzoate. • In all the 2-aminobenzoate containing compounds, the grafting reaction was detected. • The UV absorption ability was improved after the exchange reactions. • Rare earth hydroxide salts are potential matrixes to produce luminescentmore » materials. - Abstract: Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were synthesized, followed by exchange with 2-aminobenzoate. The obtained compounds were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) and ultraviolet visible (UV–vis) spectroscopies, fluorescence measurements and thermal analysis (TGA/DTA). The results from FTIR spectroscopy suggest a direct coordination of 2-aminobenzoate to the metal cations of the inorganic layered structure. The organic derivative products from the intercalation reactions absorb a broader range of UV-light in relation to that shown by the parent material; the photoluminescence measurements present a strong violet, blue and green luminescence under UV-light excitation for layered compounds with, Zn, Y and Tb, respectively. Rare earth hydroxide salts (RE-LHS) are potential alternative matrices for the immobilization of organic species to produce luminescent materials.« less

Intercalation of paracetamol into the hydrotalcite-like host

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovanda, Frantisek, E-mail: Frantisek.Kovanda@vscht.cz; Maryskova, Zuzana; Kovar, Petr

2011-12-15

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 Degree-Sign C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly nearmore » the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals. - Graphical abstract: Molecular simulations showed disordered arrangement of paracetamol molecules in the interlayer; most of the interlayer water molecules are located near the hydroxide sheets. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Paracetamol was intercalated in Mg-Al hydrotalcite-like host by rehydration/reconstruction procedure. Black-Right-Pointing-Pointer Paracetamol phenolic groups interact with positively charged sites in hydroxide sheets. Black-Right-Pointing-Pointer Molecular simulations showed disordered arrangement of guest molecules in the interlayer. Black-Right-Pointing-Pointer Slower release of paracetamol intercalated in the hydrotalcite-like host was observed.« less

Synthesis of (cinnamate-zinc layered hydroxide) intercalation compound for sunscreen application

PubMed Central

2013-01-01

Background Zinc layered hydroxide (ZLH) intercalated with cinnamate, an anionic form of cinnamic acid (CA), an efficient UVA and UVB absorber, have been synthesized by direct method using zinc oxide (ZnO) and cinnamic acid as the precursor. Results The resulting obtained intercalation compound, ZCA, showed a basal spacing of 23.9 Å as a result of cinnamate intercalated in a bilayer arrangement between the interlayer spaces of ZLH with estimated percentage loading of cinnamate of about 40.4 % w/w. The UV–vis absorption spectrum of the intercalation compound showed excellent UVA and UVB absorption ability. Retention of cinnamate in ZLH interlayers was tested against media usually came across with sunscreen usage to show low release over an extended period of time. MTT assay of the intercalation compound on human dermal fibroblast (HDF) cells showed cytotoxicity of ZCA to be concentration dependent and is overall less toxic than its precursor, ZnO. Conclusions (Cinnamate-zinc layered hydroxide) intercalation compound is suitable to be used as a safe and effective sunscreen with long UV protection effect. PMID:23383738

Intercalation of paracetamol into the hydrotalcite-like host

NASA Astrophysics Data System (ADS)

Kovanda, František; Maryšková, Zuzana; Kovář, Petr

2011-12-01

Hydrotalcite-like compounds are often used as host structures for intercalation of various anionic species. The product intercalated with the nonionic, water-soluble pharmaceuticals paracetamol, N-(4-hydroxyphenyl)acetamide, was prepared by rehydration of the Mg-Al mixed oxide obtained by calcination of hydrotalcite-like precursor at 500 °C. The successful intercalation of paracetamol molecules into the interlayer space was confirmed by powder X-ray diffraction and infrared spectroscopy measurements. Molecular simulations showed that the phenolic hydroxyl groups of paracetamol interact with hydroxide sheets of the host via the hydroxyl groups of the positively charged sites of Al-containing octahedra; the interlayer water molecules are located mostly near the hydroxide sheets. The arrangement of paracetamol molecules in the interlayer is rather disordered and interactions between neighboring molecules cause their tilting towards the hydroxide sheets. Dissolution tests in various media showed slower release of paracetamol intercalated in the hydrotalcite-like host in comparison with tablets containing the powdered pharmaceuticals.

Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

PubMed

Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

2010-11-15

Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

New layered double hydroxides by prepared by the intercalation of gibbsite

NASA Astrophysics Data System (ADS)

Rees, Jennifer R.; Burden, Chloe S.; Fogg, Andrew M.

2015-04-01

New layered double hydroxides (LDHs) with the composition [MAl4(OH)12]Cl2·1.5H2O (M=Co, Ni) have been prepared by reacting gibbsite, γ-Al(OH)3, with the appropriate chloride salt in a synthesis in which the water of crystallization is the only solvent present and fully characterized. These LDHs have been shown to undergo facile anion exchange reactions with both organic and inorganic anions at room temperature making them comparable to other LDHs in this respect. Reactions under the same conditions with CuCl2·2H2O and ZnCl2 failed to form the desired LDHs but those with nitrate salts did lead to the formation of the previously reported [MAl4(OH)12](NO3)2·1.5H2O (M=Co, Ni) compounds.

Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

PubMed

Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

2017-06-01

Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn 2 Al-Met-LDHs, identified with the formula of Zn 0.7 Al 0.3 (OH) 2 (Met) 0.3 ·0.32H 2 O, has good thermal stability. Adsorption experiments with Zn 2 Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn 2 Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn 2 Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis of highly efficient flame retardant polypropylene nanocomposites with surfactant intercalated layered double hydroxides.

PubMed

Qiu, Lei; Gao, Yanshan; Zhang, Cheng; Yan, Qinghua; O'Hare, Dermot; Wang, Qiang

2018-02-27

The thermal and flame retardant performances of polypropylene (PP) nanocomposites with sodium dodecyl sulfate (DDS) and stearic acid intercalated layered double hydroxides (DDS-LDHs and stearic-LDHs) were investigated in this study. The DDS- and stearic-LDHs were treated using the aqueous miscible organic solvent treatment (AMOST) method to give highly dispersed platelets in PP composites. The incorporation of AMO-DDS- and stearic-LDHs improved the thermal stability and flame retardancy of the PP matrix significantly. The T 0.5 (temperature at 50% weight loss) of PP/AMO-stearic-LDH (20 wt%) nanocomposites dramatically increased by 80 °C compared to that of neat PP. The flame retardant performance was dependent on both surfactants and the loading of LDHs. The AMO-stearic-LDHs showed better flame retardant properties than the AMO-DDS-LDHs, especially when the LDH loading was higher than ca. 7 wt%. In addition, stearic-LDHs with different solvothermal times including 5, 10, 24 and 72 h were studied. It was found that the nanocomposites with LDHs solvothermally treated for 10 h showed the best thermal stability. The PP/stearic-LDH (24 h) nanocomposites with 20 wt% LDH loading possessed a better flame retardant performance, with PHRR reduction reaching 70%.

Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange.

PubMed

Tamura, Hiroki; Chiba, Jun; Ito, Masahiro; Takeda, Takashi; Kikkawa, Shinichi; Mawatari, Yasuteru; Tabata, Masayoshi

2006-08-15

The formation reaction and the intercalation of adenosine triphosphate (ATP) were studied for hydrotalcite (HT), a layered double hydroxide (LDH) of magnesium and aluminum. Hydrotalcite with nitrate ions in the interlayer (HT-NO(3)) was formed (A) by dropwise addition of a solution of magnesium and aluminum nitrates (pH ca. 3) to a sodium hydroxide solution (pH ca. 14) until the pH decreased from 14 to 10 and (B) by dropwise addition of the NaOH solution to the solution of magnesium and aluminum nitrates with pH increasing from 3 to 10. The precipitate obtained with method B was contaminated with aluminum hydroxide and the crystallinity of the product was low, possibly because aluminum hydroxide precipitates at pH 4 or 5 and remains even after HT-NO(3) forms at pH above 8. With method A, however, the precipitate was pure HT-NO(3) with increased crystallinity, since the solubility of aluminum hydroxide at pH above and around 10 is high as dissolved aluminate anions are stable in this high pH region, and there was no aluminum hydroxide contamination. The formed HT-NO(3) had a composition of [Mg(0.71)Al(0.29)(OH)(2)](NO(3))(0.29).0.58H(2)O. To intercalate ATP anions into the HT-NO(3), HT-NO(3) was dispersed in an ATP solution at pH 7. It was found that the interlayer nitrate ions were completely exchanged with ATP anions by ion exchange, and the interlayer distance expanded almost twice with a free space distance of 1.2 nm. The composition of HT-ATP was established as [Mg(0.68)Al(0.32)(OH)(2)](ATP)(0.080)0.88H(2)O. The increased distance could be explained with a calculated molecular configuration of the ATP as follows: An ATP molecule is bound to an interlayer surface with the triphosphate group, the adenosine group bends owing to its bond angles and projects into the interlayer to a height of 1 nm, and the adenosine groups aligned in the interlayer support the interlayer distance.

Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

PubMed

Sen, Rupam; Bhunia, Susmita; Mal, Dasarath; Koner, Subratanath; Miyashita, Yoshitaro; Okamoto, Ken-Ichi

2009-12-01

Layered metal carboxylates [M(malonato)(H(2)O)(2)](n) (M = Ni(II) and Mn(II)) that have a claylike structure have been synthesized hydrothermally and characterized. The interlayer separation in these layered carboxylates is comparable to that of the intercalation distance of the naturally occurring clay materials or layered double hydroxides (LDHs). In this study, we have demonstrated that, instead of intercalating the metal complex into layers of the clay or LDH, layered transition metal carboxylates, [M(malonato)(H(2)O)(2)](n), as such can be used as a recyclable heterogeneous catalyst in olefin epoxidation reaction. Metal carboxylates [M(malonato)(H(2)O)(2)](n) exhibit excellent catalytic performance in olefin epoxidation reaction.

One-step synthesis of layered yttrium hydroxides in immiscible liquid-liquid systems: Intercalation of sterically-bulky hydrophobic organic anions and doping of europium ions

NASA Astrophysics Data System (ADS)

Watanabe, Mebae; Fujihara, Shinobu

2014-02-01

Inorganic-organic layered rare-earth compounds were synthesized on the basis of a biphasic liquid-liquid system in one pot. Layered yttrium hydroxides (LYHs) were chosen as a host material for the intercalation of hydrophobic organic guest anions such as benzoate, sebacate, or laurate. In a typical synthesis, an organic phase dissolving carboxylic acid was placed in contact with an equal amount of an aqueous phase dissolving yttrium nitrate n-hydrate and urea. At elevated temperatures up to 80 °C, urea was hydrolyzed to release hydroxyl anions which were used to form yttrium hydroxide layers. LYHs were then precipitated with the intercalation of carboxylate anions delivered from the organic phase under the distribution law. The structure and the morphology of the LYHs could be modulated by the intercalated anions. Doped with Eu3+ ions, the LYHs exhibited red photoluminescence which was enhanced by the intercalated anions due to the antenna effect.

Synthesis of protocatechuic acid–zinc/aluminium–layered double hydroxide nanocomposite as an anticancer nanodelivery system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barahuie, Farahnaz; Hussein, Mohd Zobir, E-mail: mzobir@upm.edu.my; Gani, Shafinaz Abd

2015-01-15

Protocatechuic acid, an active anticancer agent, has been intercalated into Zn/Al–layered double hydroxide at Zn/Al=2) using two different preparation methods, co-precipitation and ion-exchange, which are labelled as PZAE and PZAC, respectively. The release of protocatechuate from the nanocomposites occurred in a controlled manner and was fitted satisfactorily to pseudo-second order kinetics. The basal spacing of the resulting nanocomposites PZAE and PZAC was 10.2 and 11.0 Å, respectively, indicating successful intercalation of protocatechuate anions into the interlayer galleries of Zn/Al–NO{sub 3}–LDH in a monolayer arrangement with angles of 24 and 33° from the z-axis in PZAE and PZAC, respectively. The formationmore » of nanocomposites was further confirmed by a Fourier transform infrared study. Thermogravimetric and differential thermogravimetric analyses indicated that the thermal stability of the intercalated protocatechuic acid was significantly enhanced compared to its free protocatechuic acid, and the drug content in the nanocomposites was estimated to be approximately 32.6% in PZAE and 29.2% in PZAC. Both PZAE and PZAC nanocomposites inhibit the growth of human cervical, liver and colorectal cancer cell lines and exhibit no toxic effects towards normal fibroblast 3T3 cell after 72 h of treatment. - Graphical abstract: Protocatechuate anions were arranged in monolayer mode with the angle of 24° for PZAE and 33° for PZAC from Z axis to maximize interaction between carboxylate groups and brucite-like layers. - Highlights: • Two methods gave nanocomposites with slightly different physico-chemical properties. • PZAE and PZAC have the potential to be used as a controlled release formulation. • The thermal stability of PA is markedly enhanced upon the intercalation process. • Higher cancer cell growth inhibition for PZAE and PZAC nanocomposites than for PA.« less

Layered double hydroxide using hydrothermal treatment: morphology evolution, intercalation and release kinetics of diclofenac sodium

NASA Astrophysics Data System (ADS)

Joy, Mathew; Iyengar, Srividhya J.; Chakraborty, Jui; Ghosh, Swapankumar

2017-12-01

The present work demonstrates the possibilities of hydrothermal transformation of Zn-Al layered double hydroxide (LDH) nanostructure by varying the synthetic conditions. The manipulation in washing step before hydrothermal treatment allows control over crystal morphologies, size and stability of their aqueous solutions. We examined the crystal growth process in the presence and the absence of extra ions during hydrothermal treatment and its dependence on the drug (diclofenac sodium (Dic-Na)) loading and release processes. Hexagonal plate-like crystals show sustained release with ˜90% of the drug from the matrix in a week, suggesting the applicability of LDH nanohybrids in sustained drug delivery systems. The fits to the release kinetics data indicated the drug release as a diffusion-controlled release process. LDH with rod-like morphology shows excellent colloidal stability in aqueous suspension, as studied by photon correlation spectroscopy.

Recent advances in polymer supporting layered double hydroxides nanocomposite for electrochemical biosensors

NASA Astrophysics Data System (ADS)

Dhanasekaran, T.; Padmanaban, A.; Gnanamoorthy, G.; Manigandan, R.; Praveen Kumar, S.; Stephen, A.; Narayanan, V.

2018-01-01

In recent years, layered double hydroxides (LDHs) materials having emerging due to their ability of intercalate a variety of anions, either organic or inorganic molecules. The most significance of the LDHs has been found potential applications in catalysis, wastewater treatment, and electrochemical sensors. The Mg-Al LDHs (MAL) and Poly-o-phenylenediamine @ Mg-Al LDHs (P-MAL) was prepared via simple one step hydrothermal method. As prepared material was characterized using many techniques such as, the structural and crystal phase was determined from XRD and Raman analyses. The functional groups were depicted using FT-IR spectroscopy. The optical propertied studied using diffuse reflectance spectroscopy UV-vis spectroscopy and the emission property were analyzed from Photoluminescence spectroscopy. The surface morphology and average particle size was analyzed using FESEM microscopy. The prepared polymer composite material P-MAL was further used for highly sensitive electrochemical detection towards dopamine (DA).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Hui; Zou Kang; Guo Shaohuan

A nanostructural drug-inorganic clay composite involving a pharmaceutically active compound captopril (Cpl) intercalated Mg-Al-layered double hydroxides (Cpl-LDHs) with Mg/Al molar ratio of 2.06 has been assembled by coprecipitation method. Powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR) and Raman spectra analysis indicate a successful intercalation of Cpl between the layers with a vertical orientation of Cpl disulphide-containing S-S linkage. SEM photo indicates that as-synthesized Cpl-LDHs possess compact and non-porous structure with approximately and linked elliptical shape particles of ca. 50 nm. TG-DTA analyses suggest that the thermal stability of intercalated organic species is largely enhanced due to host-guest interactionmore » involving the hydrogen bond compared to pure form before intercalation. The in vitro release studies show that both the release rate and release percentages markedly decrease with increasing pH from 4.60 to 7.45 due to possible change of release mechanism during the release process. The kinetic simulation for the release data, and XRD and FT-IR analyses for samples recovered from release media indicate that the dissolution mechanism is mainly responsible for the release behaviour of Cpl-LDHs at pH 4.60, while the ion-exchange one is responsible for that at pH 7.45. - Graphical abstract: Based on XRD, FT-IR and Raman spectra analyses, it is suggested that captopril (Cpl) exists as its disulphide metabolites in the interlayer of Mg-Al-LDHs via hydrogen bonding between guest carboxylate function and hydroxyl group of the host layers. A schematic supramolecular structure of Cpl intercalates involving a vertical orientation of Cpl disulphide-containing S-S bond between the layers with carboxylate anions pointing to both hydroxide layers is presented.« less

Layered zinc hydroxide nanocones: synthesis, facile morphological and structural modification, and properties

NASA Astrophysics Data System (ADS)

Ma, Wei; Ma, Renzhi; Liang, Jianbo; Wang, Chengxiang; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2014-10-01

Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties.Layered zinc hydroxide nanocones intercalated with DS- have been synthesized for the first time via a convenient synthetic approach, using homogeneous precipitation in the presence of urea and sodium dodecyl sulfate (SDS). SDS plays a significant role in controlling the morphologies of as-synthesized samples. Conical samples intercalated with various anions were transformed through an anion-exchange route in ethanol solution, and the original conical structure was perfectly maintained. Additionally, these DS--inserted nanocones can be transformed into square-like nanoplates in aqueous solution at room temperature, fulfilling the need for different morphology-dependent properties. Corresponding ZnO nanocones and nanoplates have been further obtained through the thermal calcination of NO3--intercalating zinc hydroxide nanocones/nanoplates. These ZnO nanostructures with different morphologies exhibit promising photocatalytic properties. Electronic supplementary information (ESI) available: Typical SEM images, TGA curves and XRD patterns of as-prepared samples. See DOI: 10.1039/c4nr04166f

Dual nutraceutical nanohybrids of folic acid and calcium containing layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Hyun; Oh, Jae-Min, E-mail: jaemin.oh@yonsei.ac.kr

2016-01-15

Dual nutraceutical nanohybrids consisting of organic nutrient, folic acid (FA), and mineral nutrient, calcium, were prepared based on layered double hydroxide (LDH) structure. Among various hybridization methods such as coprecipitation, ion exchange, solid phase reaction and exfoliation-reassembly, it was found that exfoliation-reassembly was the most effective in terms of intercalation of FA moiety between Ca-containing LDH layers. X-ray diffraction patterns and infrared spectra indicated that FA molecules were well stabilized in the interlayer space of LDHs through electrostatic interaction. From the atomic force and scanning electron microscopic studies, particle thickness of LDH was determined to be varied with tens, amore » few and again tens of nanometers in pristine, exfoliated and reassembled state, respectively, while preserving particle diameter. The result confirmed layer-by-layer hybrid structure of FA and LDHs was obtained by exfoliation-reassembly. Solid UV–vis spectra showed 2-dimensional molecular arrangement of FA moiety in hybrid, exhibiting slight red shift in n→π* and π→π* transition. The chemical formulae of FA intercalated Ca-containing LDH were determined to Ca{sub 1.30}Al(OH){sub 4.6}FA{sub 0.74}·3.33H{sub 2}O and Ca{sub 1.53}Fe(OH){sub 5.06}FA{sub 2.24}·9.94H{sub 2}O by inductively coupled plasma-atomic emission spectroscopy, high performance liquid chromatography and thermogravimetry, showing high nutraceutical content of FA and Ca. - Highlights: • We successfully intercalated FA molecules into Ca-containing LDHs. • Exfoliation-reassembly was proven to be the most effective. • The interaction between LDH and FA were studied by FT-IR and UV–vis spectra. • Thermal stability of FA were enhanced by electrostatic interaction with LDH layers.« less

Layered double hydroxide intercalated with aromatic acid anions for the efficient capture of aniline from aqueous solution.

PubMed

Yu, Shujun; Wang, Xiangxue; Chen, Zhongshan; Wang, Jian; Wang, Suhua; Hayat, Tasawar; Wang, Xiangke

2017-01-05

Aniline is toxic and hard to be degraded, and thereby causes the environmental pollution seriously. Herein, a practical and green hydrothermal method was applied to fabricate terephthalic acid and pyromellitic acid intercalated layered double hydroxides (LDH) (named as TAL and PAL) for aniline efficient removal. The sorption of aniline on LDH-based materials were investigated at different experimental conditions, and the results indicated that aniline sorption on LDH, TAL and PAL were strongly dependent on pH and independent of ionic strength. The maximum sorption capacities of aniline on TAL and PAL at pH 5.0 and 293K were 90.4 and 130.0mg/g, respectively, which were significantly higher than that of aniline on LDH (52.6mg/g). Based on the BET, FTIR and XPS analysis, the higher sorption capacities of TAL and PAL were mainly due to high surface area and basal spacing as well as the abundant functional groups (e.g. -COO - ). The interactions of aniline with TAL and PAL were mainly dominated by hydrogen bonds and electrostatic interactions. Such a facile synthesis method, efficient removal performance and superior reusability indicated that the aromatic acid modified LDH materials had potential application for efficient treatment of organic pollutants in environmental pollution cleanup. Copyright © 2016 Elsevier B.V. All rights reserved.

Delivery system for mefenamic acid based on the nanocarrier layered double hydroxide: Physicochemical characterization and evaluation of anti-inflammatory and antinociceptive potential.

PubMed

Cunha, Vanessa R R; Guilherme, Viviane A; de Paula, Eneida; de Araujo, Daniele R; Silva, Renan O; Medeiros, Jand V R; Leite, José R S A; Petersen, Philippe A D; Foldvari, Marianna; Petrilli, Helena M; Constantino, Vera R L

2016-01-01

The anionic form of the drug mefenamic acid intercalated into the nanocarrier layered double hydroxide (LDH-Mef) was evaluated by anti-inflammatory and antinociceptive assays. The LDH-Mef material was characterized by a set of physicochemical techniques, which was supported by Density Functional Theory calculations. The pharmacological effects of LDH-Mef (40 wt% of drug) were evaluated by hemolytic, anti-inflammatory activity and antinociceptive assays. In vivo assays were conducted for the first time in order to assess the LDH-Mef potential. The hemolytic effects decreased for the intercalated Mef as demonstrated by the higher tolerated hemolytic concentration (1.83 mM) compared to mefenamic acid (MefH), 0.48 mM. Pretreatment of animals with MefH or LDH-Mef reduced carrageenan-, dextran sulfate- and PGE2-induced paw edema. MefH or LDH-Mef also decrease total leucocytes and neutrophil counts of the peritoneal cavity after inflammation induction with carrageenan. In the nociception model, oral pretreatment with LDH-Mef reduced mechanical hypernociception carrageenan-induced after 3-4h and also the number of writhings induced by acetic acid. This work shows the increase of the anti-inflammatory and antinociceptive potential of the drug confined into the LDH, as well as, its hemolytic effect. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and characterization of sulfate and dodecylbenzenesulfonate intercalated zinc iron layered double hydroxides by one-step coprecipitation route

NASA Astrophysics Data System (ADS)

Zhang, Hui; Wen, Xing; Wang, Yingxia

2007-05-01

Inorganic sulfate- and organic dodecylbenzenesulfonate (DBS)-intercalated zinc-iron layered double hydroxides (LDHs) materials were prepared by one-step coprecipitation method from a mixed salt solutions containing Zn(II), Fe(II) and Fe(III) salts. The as-prepared samples have been characterized by X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), low-temperature nitrogen adsorption, scanning electron microscopy (SEM), inductively coupled plasma emission spectroscopy (ICP), and Mössbauer spectroscopy (MS). The XRD analyses demonstrate the typical LDH-like layered structural characteristics of both products. The room temperature MS results reveal the characteristics of both the Fe(II) and Fe(III) species for SO 42--containing product, while only the Fe(III) characteristic for DBS-containing one. The combination characterization results and Rietveld analysis illustrate that the SO 42--containing product possesses the Green Rust two (GR2)-like crystal structure with an approximate chemical composition of [Zn 0.435·Fe II0.094·Fe III0.470·(OH) 2]·(SO 42-) 0.235·1.0H 2O, while the DBS-containing one exhibits the common LDH compound-like structure. The contact angle measurement indicates the evident hydrophobic properties of DBS-containing nanocomposite, compared with SO 42--containing product, due to the modification of the internal and external surface of LDHs by the organic hydrophobic chain of DBS.

Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

NASA Astrophysics Data System (ADS)

Barahuie, Farahnaz; Hussein, Mohd Zobir; Arulselvan, Palanisamy; Fakurazi, Sharida; Zainal, Zulkarnain

2014-09-01

A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the properties of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro.

Controlled release formulation of an anti-depression drug based on a L-phenylalanate-zinc layered hydroxide intercalation compound

NASA Astrophysics Data System (ADS)

Hashim, Norhayati; Sharif, Sharifah Norain Mohd; Isa, Illyas Md; Hamid, Shahidah Abdul; Hussein, Mohd Zobir; Bakar, Suriani Abu; Mamat, Mazidah

2017-06-01

The intercalation of L-phenylalanate (LP) into the interlayer gallery of zinc layered hydroxide (ZLH) has been successfully executed using a simple direct reaction method. The synthesised intercalation compound, zinc layered hydroxide-L-phenylalanate (ZLH-LP), was characterised using PXRD, FTIR, CHNS, ICP-OES, TGA/DTG, FESEM and TEM. The PXRD patterns of the intercalation compound demonstrate an intense and symmetrical peak, indicating a well-ordered crystalline layered structure. The appearance of an intercalation peak at a low angle of 2θ with a basal spacing of 16.3 Å, signifies the successful intercalation of the L-phenylalanate anion into the interlayer gallery of the host. The intercalation is also validated by FTIR spectroscopy and CHNS elemental analysis. Thermogravimetric analysis confirms that the ZLH-LP intercalation compound has higher thermal stability than the pristine L-phenylalanine. The observed percentage of L-phenylalanate accumulated release varies in each release media, with 84.5%, 79.8%, 63.8% and 61.8% release in phosphate buffer saline (PBS) solution at pH 4.8, deionised water, PBS solution at pH 7.4 and NaCl solution, respectively. The release behaviour of LP from its intercalation compounds in deionised water and PBS solution at pH 4.8 follows pseudo second order, whereas in NaCl solution and PBS solution at pH 7.4, it follows the parabolic diffusion model. This study shows that the synthesised ZLH-LP intercalation compound can be used for the formation of a new generation of materials for targeted drug release with controlled release properties.

Use of anionic clays for photoprotection and sunscreen photostability: Hydrotalcites and phenylbenzimidazole sulfonic acid

NASA Astrophysics Data System (ADS)

Perioli, Luana; Ambrogi, Valeria; Rossi, Carlo; Latterini, Loredana; Nocchetti, Morena; Costantino, Umberto

2006-05-01

Layered double hydroxides of hydrotalcite (HTlc) type have many applications as matrices in pharmaceutical and cosmetic fields when intercalated with active species in anionic form. The aim of this work was to intercalate 2-phenyl-1H-benzimidazole-5-sulfonic acid (Eusolex 232) (EUS) as sunscreen molecule into hydrotalcites in order to obtain the sunscreen stabilization, the reduction of its photodegradation and the elimination of close contact between skin and filter. Hydrotalcites MgAl and ZnAl were used as hosts and the intercalation products obtained were characterized by TG, RX and DSC. They were also submitted to spectrophotometric assays in order to study the matrix influence on sunlight protection and on sunscreen photostability. These experiments showed that both MgAl and ZnAl HTlc intercalation products maintained the sunscreen properties and eusolex photodegradation was reduced. The in vitro EUS release from both formulations was almost negligible when compared with formulations containing free EUS. The EUS intercalation in HTlc and the respective formulations provided advantages in the maintenance of photoprotection efficacy, filter photostabilization and avoidance of a close contact between skin and filter, with consequent elimination of allergy problems and photocross reactions.

Herbicide-Intercalated Zinc Layered Hydroxide Nanohybrid for a Dual-Guest Controlled Release Formulation

PubMed Central

Hussein, Mohd Zobir; Rahman, Nor Shazlirah Shazlyn Abdul; Sarijo, Siti H.; Zainal, Zulkarnain

2012-01-01

Herbicides, namely 4-(2,4-dichlorophenoxy) butyrate (DPBA) and 2-(3-chlorophenoxy) propionate (CPPA), were intercalated simultaneously into the interlayers of zinc layered hydroxide (ZLH) by direct reaction of zinc oxide with both anions under aqueous environment to form a new nanohybrid containing both herbicides labeled as ZCDX. Successful intercalation of both anions simultaneously into the interlayer gallery space of ZLH was studied by PXRD, with basal spacing of 28.7 Å and supported by FTIR, TGA/DTG and UV-visible studies. Simultaneous release of both CPPA and DPBA anions into the release media was found to be governed by a pseudo second-order equation. The loading and percentage release of the DPBA is higher than the CPPA anion, which indicates that the DPBA anion was preferentially intercalated into and released from the ZLH interlayer galleries. This work shows that layered single metal hydroxide, particularly ZLH, is a suitable host for the controlled release formulation of two herbicides simultaneously. PMID:22837696

Release behavior and toxicity profiles towards A549 cell lines of ciprofloxacin from its layered zinc hydroxide intercalation compound.

PubMed

Abdul Latip, Ahmad Faiz; Hussein, Mohd Zobir; Stanslas, Johnson; Wong, Charng Choon; Adnan, Rohana

2013-01-01

Layered hydroxides salts (LHS), a layered inorganic compound is gaining attention in a wide range of applications, particularly due to its unique anion exchange properties. In this work, layered zinc hydroxide nitrate (LZH), a family member of LHS was intercalated with anionic ciprofloxacin (CFX), a broad spectrum antibiotic via ion exchange in a mixture solution of water:ethanol. Powder x-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the drug anions were successfully intercalated in the interlayer space of LZH. Specific surface area of the obtained compound was increased compared to that of the host due to the different pore textures between the two materials. CFX anions were slowly released over 80 hours in phosphate-buffered saline (PBS) solution due to strong interactions that occurred between the intercalated anions and the host lattices. The intercalation compound demonstrated enhanced antiproliferative effects towards A549 cancer cells compared to the toxicity of CFX alone. Strong host-guest interactions between the LZH lattice and the CFX anion give rise to a new intercalation compound that demonstrates sustained release mode and enhanced toxicity effects towards A549 cell lines. These findings should serve as foundations towards further developments of the brucite-like host material in drug delivery systems.

Synthesis of ktenasite, a double hydroxide of zinc and copper, and its intercalation reaction

NASA Astrophysics Data System (ADS)

Xue, Mei; Chitrakar, Ramesh; Sakane, Kohji; Ooi, Kenta; Kobayashi, Shoichi; Ohnishi, Masayuki; Doi, Akira

2004-04-01

Ktenasite was synthesized by the simple method of mixing ZnO powder with CuSO 4 solution at room temperature. The X-ray diffraction pattern of synthesized ktenasite was very similar to that of mineral ktenasite. The lattice parameters were determined as a=0.559, b=0.616, c=2.374 nm and β=95.63°, which agreed comparatively well with those for mineral ktenasite. The synthesized ktenasite consisted of thin rectangular particles ranging in size from 2 to 4 μm in length. TEM observation suggested the formation of a super lattice structure in the a-axis direction and significant crystal growth in the b-axis direction. The intercalation reaction of sodium dodecyl sulfate (NaDS) with ktenasite showed that the intercalation took place accompanied by the expansion of basal spacing from 1.17 to 2.70 nm. The reaction progressed by the SO 42-/DS - anion exchange mechanism with the dissolution of interlayer [Zn(H 2O) 6]SO 4 salt.

Superconductivity and magnetism in iron sulfides intercalated by metal hydroxides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05268a Click here for additional data file.

PubMed Central

Zhou, Xiuquan; Eckberg, Christopher; Wilfong, Brandon; Liou, Sz-Chian; Vivanco, Hector K.; Paglione, Johnpierre

2017-01-01

Inspired by naturally occurring sulfide minerals, we present a new family of iron-based superconductors. A metastable form of FeS known as the mineral mackinawite forms two-dimensional sheets that can be readily intercalated by various cationic guest species. Under hydrothermal conditions using alkali metal hydroxides, we prepare three different cation and metal hydroxide-intercalated FeS phases including (Li1–xFexOH)FeS, [(Na1–xFex)(OH)2]FeS, and KxFe2–yS2. Upon successful intercalation of the FeS layer, the superconducting critical temperature T c of mackinawite is enhanced from 5 K to 8 K for the (Li1–xFexOH)δ+ intercalate. Layered heterostructures of [(Na1–xFex)(OH)2]FeS resemble the natural mineral tochilinite, which contains an iron square lattice interleaved with a hexagonal hydroxide lattice. Whilst heterostructured [(Na1–xFex)(OH)2]FeS displays long-range magnetic ordering near 15 K, KxFe2–yS2 displays short range antiferromagnetism. PMID:28580110

Anticancer Activity of Ferulic Acid-Inorganic Nanohybrids Synthesized via Two Different Hybridization Routes, Reconstruction and Exfoliation-Reassembly

PubMed Central

Choi, Ae-Jin; Oh, Jae-Min

2013-01-01

We have successfully prepared nanohybrids of biofunctional ferulic acid and layered double hydroxide nanomaterials through reconstruction and exfoliation-reassembly routes. From X-ray diffraction and infrared spectroscopy, both nanohybrids were determined to incorporate ferulic acid molecules in anionic form. Micrsocopic results showed that the nanohybrids had average particle size of 150 nm with plate-like morphology. As the two nanohybridization routes involved crystal disorder and random stacking of layers, the nanohybrids showed slight alteration in z-axis crystallinity and particle size. The zeta potential values of pristine and nanohybrids in deionized water were determined to be positive, while those in cell culture media shifted to negative values. According to the in vitro anticancer activity test on human cervical cancer HeLa cells, it was revealed that nanohybrids showed twice anticancer activity compared with ferulic acid itself. Therefore we could conclude that the nanohybrids of ferulic acid and layered double hydroxide had cellular delivery property of intercalated molecules on cancer cell lines. PMID:24453848

Self-healing Li-Al layered double hydroxide conversion coating modified with aspartic acid for 6N01 Al alloy

NASA Astrophysics Data System (ADS)

Zhang, Caixia; Luo, Xiaohu; Pan, Xinyu; Liao, Liying; Wu, Xiaosong; Liu, Yali

2017-02-01

A self-healing Li-Al layered double hydroxide conversion coating (LCC) modified with aspartic acid (ALCC) was prepared on 6N01 Al alloy for corrosion protection. Scanning electron microscopy (SEM) showed that a compact thin film has been successfully formed on the alloy. X-ray diffraction (XRD) and FT-IR spectra proved that species of aspartic acid anions were successfully intercalated into LCC. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and neutral salt spray (NSS) testing showed that the resultant ALCC could provide effective corrosion protection for the Al alloy. During immersion of the ALCC-coated alloy in 3.5% NaCl solution, new film was formed in the area of artificially introduced scratch, indicating its self-healing capability. XPS results demonstrated that Cl- anions exchange partial Asp anions according to the change content of element on conversion coating. From the above results, the possible mechanism via exchange/self-assembly was proposed to illustrate the phenomenon of self-healing.

Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents.

PubMed

Li, Changming; Wei, Min; Evans, David G; Duan, Xue

2014-11-01

Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anticancer activity of ferulic acid-inorganic nanohybrids synthesized via two different hybridization routes, reconstruction and exfoliation-reassembly.

PubMed

Kim, Hyoung-Jun; Ryu, Kitae; Kang, Joo-Hee; Choi, Ae-Jin; Kim, Tae-il; Oh, Jae-Min

2013-01-01

We have successfully prepared nanohybrids of biofunctional ferulic acid and layered double hydroxide nanomaterials through reconstruction and exfoliation-reassembly routes. From X-ray diffraction and infrared spectroscopy, both nanohybrids were determined to incorporate ferulic acid molecules in anionic form. Microscopic results showed that the nanohybrids had average particle size of 150 nm with plate-like morphology. As the two nanohybridization routes involved crystal disorder and random stacking of layers, the nanohybrids showed slight alteration in z-axis crystallinity and particle size. The zeta potential values of pristine and nanohybrids in deionized water were determined to be positive, while those in cell culture media shifted to negative values. According to the in vitro anticancer activity test on human cervical cancer HeLa cells, it was revealed that nanohybrids showed twice anticancer activity compared with ferulic acid itself. Therefore we could conclude that the nanohybrids of ferulic acid and layered double hydroxide had cellular delivery property of intercalated molecules on cancer cell lines.

Laccase electrodes based on the combination of single-walled carbon nanotubes and redox layered double hydroxides: Towards the development of biocathode for biofuel cells

NASA Astrophysics Data System (ADS)

Ding, Shou-Nian; Holzinger, Michael; Mousty, Christine; Cosnier, Serge

Single-walled carbon nanotubes (SWCNT) were combined with layered double hydroxides (LDH) intercalated with 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonate) diammonium salt [ZnCr-ABTS] to entrap and electrically connect laccase enzyme. The resulting laccase electrodes exhibited an electro-enzymatic activity for O 2 reduction. To improve this electrocatalytic activity, varying SWCNT quantities and loading methods were tested to optimize the configuration of the laccase electrodes. Furthermore, the resulting bioelectrode was successfully used as a biocathode for the elaboration of a membrane-less glucose/air biofuel cell. In 0.1 M phosphate buffer (PBS) of pH 6.0, containing glucose (5 mM) under ambient conditions, the assembled biofuel cell yielded a maximum power density of 18 μW cm -2 at a cell voltage of 0.3 V whereas this power decreased to 8.3 μW cm -2 for a biofuel cell based on the identical biocathode setup without SWCNT.

Preparation, physicochemical characterisation and magnetic properties of Cu-Al layered double hydroxides with CO 32- and anionic surfactants with different alkyl chains in the interlayer

NASA Astrophysics Data System (ADS)

Trujillano, Raquel; Holgado, María Jesús; Pigazo, Fernando; Rives, Vicente

2006-03-01

Layered double hydroxides with the hydrotalcite-like structure, containing Cu(II) and Al(III) in the layers, and different alkyl sulphonates in the interlayer, have been prepared and characterised by powder X-ray diffraction, FT-IR spectroscopy, differential thermal analysis and thermogravimetric analysis. Their magnetic properties have been also studied. Except for the sample containing octadecanesulphonate in the interlayer, for which an excess of sulphonate exists, pure crystalline phases have been obtained in the other cases. Upon heating, combustion of the organic chain takes place at lower temperature than for the corresponding sodium salts. A two-dimensional antiferromagnetic behaviour is observed at 200 K in all samples containing intercalated sulphonate. The χT value is lower for the samples containing interlayer sulphonates (with layer-layer distances in the 21-31 Å range), than for a carbonate-containing analogue (basal spacing 7.51 Å).

MgAl- Layered Double Hydroxide Nanoparticles for controlled release of Salicylate.

PubMed

Mondal, Soumini; Dasgupta, Sudip; Maji, Kanchan

2016-11-01

Layered double hydroxides (LDHs), have been known for many decades as catalyst and ceramic precursors, traps for anionic pollutants, and additives for polymers. Recently, their successful synthesis on the nanometer scale opened up a whole new field for their application in nanomedicine. Here we report the efficacy of Mg1-xAlx (NO3)x (OH)2 LDH nanoparticles as a carrier and for controlled release of one of the non-steroidal anti-inflammatory drugs (NSAID), sodium salicylate. Mg1-xAlx (NO3)x (OH)2.nH2O nanoparticles were synthesized using co-precipitation method from an aqueous solution of Mg(NO3)2.6H2O and Al(NO3)3.9H2O. Salicylate was intercalated in the interlayer space of Mg-Al LDH after suspending nanoparticles in 0.0025(M) HNO3 and 0.75 (M) NaNO3 solution and using anion exchange method under N2 atmosphere. The shift in the basal planes like (003) and (006) to lower 2θ value in the XRD plot of intercalated sample confirmed the increase in basal spacing in LDH because of intercalation of salicylate into the interlayer space of LDH. FTIR spectroscopy of SA-LDH nano hybrid revealed a red shift in the frequency band of carboxylate group in salicylate indicating an electrostatic interaction between cationic LDH sheet and anionic drug. Differential thermal analysis of LDH-SA nanohybrid indicated higher thermal stability of salicylate in the intercalated form into LDH as compared to its free state. DLS studies showed a particle size distribution between 30-60 nm for pristine LDH whereas salicylate intercalated LDH exhibited a particle size distribution between 40-80nm which is ideal for its efficacy as a superior carrier for drugs and biomolecules. The cumulative release kinetic of salicylate from MgAl-LDH-SA hybrids in phosphate buffer saline (PBS) at pH7.4 showed a sustained release of salicylate up to 72h that closely resembled first order release kinetics through a combination of drug diffusion and dissolution of LDH under physiological conditions. Also the cytotoxicity tests performed revealed the less toxic nature of the nanohybrid as compared to the bare SA drug. Copyright © 2016 Elsevier B.V. All rights reserved.

Rapid mass production of two-dimensional metal oxides and hydroxides via the molten salts method

PubMed Central

Hu, Zhimi; Xiao, Xu; Jin, Huanyu; Li, Tianqi; Chen, Ming; Liang, Zhun; Guo, Zhengfeng; Li, Jia; Wan, Jun; Huang, Liang; Zhang, Yanrong; Feng, Guang; Zhou, Jun

2017-01-01

Because of their exotic electronic properties and abundant active sites, two-dimensional (2D) materials have potential in various fields. Pursuing a general synthesis methodology of 2D materials and advancing it from the laboratory to industry is of great importance. This type of method should be low cost, rapid and highly efficient. Here, we report the high-yield synthesis of 2D metal oxides and hydroxides via a molten salts method. We obtained a high-yield of 2D ion-intercalated metal oxides and hydroxides, such as cation-intercalated manganese oxides (Na0.55Mn2O4·1.5H2O and K0.27MnO2·0.54H2O), cation-intercalated tungsten oxides (Li2WO4 and Na2W4O13), and anion-intercalated metal hydroxides (Zn5(OH)8(NO3)2·2H2O and Cu2(OH)3NO3), with a large lateral size and nanometre thickness in a short time. Using 2D Na2W4O13 as an electrode, a high performance electrochemical supercapacitor is achieved. We anticipate that our method will enable new path to the high-yield synthesis of 2D materials for applications in energy-related fields and beyond. PMID:28555669

Organic-inorganic hybrid nanocomposites based on chitosan derivatives and layered double hydroxides with intercalated phacolysin as ocular delivery system

NASA Astrophysics Data System (ADS)

Qin, Zhiguo; Zhang, Jie; Chi, Huibo; Cao, Feng

2015-12-01

This study was mainly aimed to evaluate the potential use of a novel ocular drug delivery system, organic-inorganic hybrid nanocomposites based on chitosan derivatives and layered double hydroxides (LDH). Organic polymers of chitosan-glutathione (CG) and pre-activated chitosan-glutathione (CG-2MNA) were successfully synthesized and characterized. LDH with intercalated phacolysin (PCL), including larger hexagonal LDH-PCL (Lh-LDH-PCL), larger spherical LDH-PCL (Ls-LDH-PCL), smaller hexagonal LDH-PCL (Sh-LDH-PCL), CG hybrid LDH-PCL (LDH-PCL-CG), and CG-2MNA hybrid LDH-PCL (LDH-PCL-CG-2MNA), were prepared. The nanocomposites with particle size of 107.2-274.9 nm were characterized by powder X-ray diffraction, Fourier transform infrared, transmission electron micrographs, etc. In vivo precorneal retention studies showed that the detectable time of all nanocomposites was prolonged from 2 to 6 h in comparison to PCL saline. Accordingly, the AUC0-6h values of Lh-LDH-PCL, Ls-LDH-PCL, Sh-LDH-PCL, LDH-PCL-CG, and LDH-PCL-CG-2MNA nanocomposites were increased by 2.27-, 2.08-, 3.08-, 4.67-, and 3.36-fold, respectively. The Draize test and hematoxylin and eosin staining demonstrated that modified LDH had no eye irritation after single and repeated administration. These results indicated that chitosan derivatives-LDH hybrid nanocomposite dispersion could be a promising ocular drug delivery system to improve precorneal retention time of drugs.

Advanced bifunctional electrocatalyst generated through cobalt phthalocyanine tetrasulfonate intercalated Ni2Fe-layered double hydroxides for a laminar flow unitized regenerative micro-cell

NASA Astrophysics Data System (ADS)

Zhong, Haihong; Tian, Ran; Gong, Xiaoman; Li, Dianqing; Tang, Pinggui; Alonso-Vante, Nicolas; Feng, Yongjun

2017-09-01

We fabricated a NiFeOx/CoNy-C nanocomposite derived from CoPcTs-intercalated Ni2Fe-layered double hydroxides (Ni2Fe-CoPcTs-LDH), which served as high-efficiency, low-cost, and long-durability bifunctional oxygen electrocatalyst in half-cell, and a H2-O2 laminar flow unitized regenerative micro-cell (LFURMC) in alkaline media. Based on the synergistic effect between Co-Ny and NiFeOx centers, the non-noble hybrid catalyst NiFeOx/CoNy-C achieves a ΔE (η@jOER,10 - η@jORR,-3) = 0.84 V in alkaline solution, outperforming the commercial Pt/C, and very close to that of IrOx/C. In the fuel cell mode, the performance of NiFeOx/CoNy-C with the maximum power density of 56 mW cm-2 is similar to that of Pt/C (63 mW cm-2) and IrOx/C (58 mW cm-2); in the electrolysis mode, the calculated maximum electrical power consumed on NiFeOx/CoNy-C (237 mW cm-2) is more than 3 times that on Pt/C (73 mW cm-2), similar with that of IrOx/C. More importantly, the NiFeOx/CoNy-C shows a remarkable stability in alternating modes in a LFURMC system.

Synthesis of layered double hydroxide nanosheets by coprecipitation using a T-type microchannel reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pang, Xiujiang; Sun, Meiyu; Ma, Xiuming

The synthesis of Mg{sub 2}Al–NO{sub 3} layered double hydroxide (LDH) nanosheets by coprecipitation using a T-type microchannel reactor is reported. Aqueous LDH nanosheet dispersions were obtained. The LDH nanosheets were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy and particle size analysis, and the transmittance and viscosity of LDH nanosheet dispersions were examined. The two-dimensional LDH nanosheets consisted of 1–2 brucite-like layers and were stable for ca. 16 h at room temperature. In addition, the co-assembly between LDH nanosheets and dodecyl sulfate (DS) anions was carried out, and a DS intercalated LDH nanohybrid was obtained. To the bestmore » of our knowledge, this is the first report of LDH nanosheets being directly prepared in bulk aqueous solution. This simple, cheap method can provide naked LDH nanosheets in high quantities, which can be used as building blocks for functional materials. - Graphical abstract: Layered double hydroxide (LDH) nanosheets were synthesized by coprecipitation using a T-type microchannel reactor, and could be used as basic building blocks for LDH-based functional materials. Display Omitted - Highlights: • LDH nanosheets were synthesized by coprecipitation using a T-type microchannel reactor. • Naked LDH nanosheets were dispersed in aqueous media. • LDH nanosheets can be used as building blocks for functional materials.« less

Study of 2,4-dichlorophenoxyacetic acid (2,4-D) removal by Cu-Fe-layered double hydroxide from aqueous solution

NASA Astrophysics Data System (ADS)

Nejati, Kamellia; Davary, Soheila; Saati, Marziye

2013-09-01

The hydrotalcite-like compound of Cu-Fe-layered double hydroxide was studied as a potential adsorbent of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The nanoparticles of Cu-Fe layered double hydroxide were prepared by Cu/Fe molar ratio of 2:1 using a coprecipitation method at pH 8.5 and characterized by the X-ray powder diffraction (XRD), the Fourier transform infrared spectroscopy (FT-IR), the thermal gravimetric analysis (TGA) and the elemental analysis. The size and morphology of nanoparticles were examined by the transmission electron microscopy (TEM). The adsorption experiments on LDH, on the other hand, were conducted in three different procedures, namely, time-dependent, pH-dependent and temperature-dependent. Characterization of the adsorption products by the XRD method indicates that the intercalation of 2,4-D between the LDH layers has not occurred and the surface adsorption had taken place. The adsorption kinetic was tested for pseudo-first-order, pseudo-second-order, Elovich and Intra-particle diffusion kinetic models and the rate constants were calculated. The equilibrium adsorption data were described by Langmuir and Freundlich equations. It was observed that, the Langmuir isotherm slightly better fitted to the experimental data rather than that of Freundlich. In the adsorption experiments, the Gibbs free energy values, ΔG°, the enthalpy, ΔH°, and the entropy, ΔS° were also determined.

Release behavior and toxicity profiles towards A549 cell lines of ciprofloxacin from its layered zinc hydroxide intercalation compound

PubMed Central

2013-01-01

Background Layered hydroxides salts (LHS), a layered inorganic compound is gaining attention in a wide range of applications, particularly due to its unique anion exchange properties. In this work, layered zinc hydroxide nitrate (LZH), a family member of LHS was intercalated with anionic ciprofloxacin (CFX), a broad spectrum antibiotic via ion exchange in a mixture solution of water:ethanol. Results Powder x-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA) confirmed the drug anions were successfully intercalated in the interlayer space of LZH. Specific surface area of the obtained compound was increased compared to that of the host due to the different pore textures between the two materials. CFX anions were slowly released over 80 hours in phosphate-buffered saline (PBS) solution due to strong interactions that occurred between the intercalated anions and the host lattices. The intercalation compound demonstrated enhanced antiproliferative effects towards A549 cancer cells compared to the toxicity of CFX alone. Conclusions Strong host-guest interactions between the LZH lattice and the CFX anion give rise to a new intercalation compound that demonstrates sustained release mode and enhanced toxicity effects towards A549 cell lines. These findings should serve as foundations towards further developments of the brucite-like host material in drug delivery systems. PMID:23849189

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

Intercalation of cellulase enzyme into a hydrotalcite layer structure

NASA Astrophysics Data System (ADS)

Zou, N.; Plank, J.

2015-01-01

A new inorganic-organic hybrid material whereby cellulase enzyme is incorporated into a hydrotalcite type layered double hydroxide (LDH) structure is reported. The Mg2Al-cellulase-LDH was synthesized via co-precipitation from Mg/Al nitrate at pH=9.6. Characterization was performed using X-ray powder diffraction (XRD), small angle X-ray scattering (SAXS), elemental analysis, infrared spectroscopy (IR) and thermogravimetry (TG). From XRD and SAXS measurements, a d-value of ~5.0 nm was identified for the basal spacing of the Mg2Al-cellulase-LDH. Consequently, the cellulase enzyme (hydrodynamic diameter ~6.6 nm) attains a slightly compressed conformation when intercalated. Formation of the LDH hybrid was also confirmed via scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mg2Al-cellulase-LDH phases appear as ~20 nm thin foils which are intergrown to flower-like aggregates. Activity of the enzyme was retained after deintercalation from the Mg2Al-LDH framework using anion exchange. Accordingly, cellulase is not denatured during the intercalation process, and LDH presents a suitable host structure for time-controlled release of the biomolecule.

Efficient delivery of anticancer drug MTX through MTX-LDH nanohybrid system

NASA Astrophysics Data System (ADS)

Oh, Jae-Min; Park, Man; Kim, Sang-Tae; Jung, Jin-Young; Kang, Yong-Gu; Choy, Jin-Ho

2006-05-01

We have been successful to intercalate anticancer drug, methotrexate (MTX), into layered double hydroxides (LDHs), Mg2Al(OH)6(NO3)·0.1H2O, through conventional co-precipitation method. Layered double hydroxides (LDHs) are endowed with great potential for delivery vector, since their cationic layers lead to safe reservation of biofunctional molecules such as drug molecules or genes. And their ion exchangeability and solubility in acidic media (pH<4) give rise to the controlled release of drug molecules. Moreover, it has been partly confirmed that LDH itself is non-toxic and facilitate the cellular permeation. To check the toxicity of LDHs, the osteosarcoma cell culture lines (Saos-2 and MG-63) and the normal one (human fibroblast) were used for in vitro test. The anticancer efficacy of MTX intercalated LDHs (MTX-LDH nanohybrids) was also estimated in vitro by the bioassay such as MTT and BrdU (5-bromo-2-deoxyuridine) with the bone cancer cell culture lines (Saos-2 and MG-63). According to the toxicity test results, LDHs do not harm to both the normal and cancer cells upto the concentration of 500 ug/mL. The anticancer efficacy test for the MTX-LDH nanohybrids turn out to be much more effective in cell suppression compared to the MTX itself. According to the cell-line tests, the MTX-LDH shows same drug efficacy to the MTX itself in spite of the low concentration by ˜5000 times. Such a high cancer suppression effect of MTX-LDH hybrid is surely due to the excellent delivery efficiency of inorganic delivery vector, LDHs.

Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbajal Arizaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.m; Wypych, Fernando; Castillon Barraza, Felipe

2010-10-15

A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia,more » the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.« less

Organo/Zn-Al LDH Nanocomposites for Cationic Dye Removal from Aqueous Media

NASA Astrophysics Data System (ADS)

Starukh, G.; Rozovik, O.; Oranska, O.

2016-04-01

Cationic dye sorption by Zn-Al-layered double hydroxides (LDHs) modified with anionic surfactants was examined using methylene blue (MB) dye as a compound model in aqueous solutions. The modification of Zn-Al LDHs was performed by reconstruction method using dodecyl sulfate anion (DS) solutions. DS contained Zn-Al LDHs were characterized by XRD, FTIR, thermogravimetric, and SEM analysis. The reconstructed organo/Zn-Al LDHs comprise the crystalline phases (DS-intercalated LDHs, hydrotalcite), and the amorphous phase. The intercalation of DS ions into the interlayer galleries and DS adsorption on the surface of the LDHs occurred causing the MB adsorption on the external and its sorption in the internal surfaces of modified LDHs. The presence of DS greatly increased the affinity of organo/Zn-Al LDHs for MB due to hydrophobic interactions between the surfactants and the dye molecules. The optical properties of sorbed MB were studied.

Intercalation of sulfonated melamine formaldehyde polycondensates into a hydrocalumite LDH structure

NASA Astrophysics Data System (ADS)

von Hoessle, F.; Plank, J.; Leroux, F.

2015-05-01

A series of sulfonated melamine formaldehyde (SMF) polycondensates possessing different anionic charge amounts and molecular weights was synthesized and incorporated into a hydrocalumite type layered double hydroxide structure using the rehydration method. For this purpose, tricalcium aluminate was dispersed in water and hydrated in the presence of these polymers. Defined inorganic-organic hybrid materials were obtained as reaction products. All SMF polymers tested intercalated readily into the hydrocalumite structure, independent of their different molecular weights (chain lengths) and anionic charge amounts. X-ray diffraction revealed typical patterns for weakly ordered, highly polymer loaded LDH materials which was confirmed via elemental analysis and thermogravimetry. IR spectroscopy suggests that the SMF polymers are interleaved between the [Ca2Al(OH)6]+ main sheets via electrostatic interaction, and that no chemical bond between the host matrix and the guest anion is formed. The SMF polymers well ensconced within the LDH structure exhibit significantly slower thermal degradation.

Cellular trafficking of low molecular weight heparin incorporated in layered double hydroxide nanoparticles in rat vascular smooth muscle cells.

PubMed

Gu, Zi; Rolfe, Barbara E; Thomas, Anita C; Campbell, Julie H; Lu, G Q Max; Xu, Zhi P

2011-10-01

This paper reports a clear elucidation of the pathway for the cellular delivery of layered double hydroxide (LDH) nanoparticles intercalated with anti-restenotic low molecular weight heparin (LMWH). Cellular uptake of LMWH-LDH conjugates into cultured rat vascular smooth muscle cells (SMCs) measured via flow cytometry was more than ten times greater than that of LMWH alone. Confocal and transmission electron microscopy showed LMWH-LDH conjugates taken up by endosomes, then released into the cytoplasm. We propose that LMWH-LDH is taken up via a unique 'modified endocytic' pathway, whereby the conjugate is internalized by SMCs in early endosomes, sorted in late endosomes, and quickly released from late endosomes/lysosomes, avoiding degradation. Treatment of cells with LMWH-LDH conjugates suppressed the activation of ERK1/2 in response to foetal calf serum (FCS) for up to 24h, unlike unconjugated LMWH which had no significant effect at 24h. Improved understanding of the intracellular pathway of LMWH-LDH nanohybrids in SMC will allow for refinement of design for LDH nanomedicine applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

Ultrasonically-enhanced preparation, characterization of CaFe-layered double hydroxides with various interlayer halide, azide and oxo anions (CO32-, NO3-, ClO4-).

PubMed

Szabados, Márton; Varga, Gábor; Kónya, Zoltán; Kukovecz, Ákos; Carlson, Stefan; Sipos, Pál; Pálinkó, István

2018-01-01

An ultrasonically-enhanced mechanochemical method was developed to synthesize CaFe-layered double hydroxides (LDHs) with various interlayer anions (CO 3 2- , NO 3 - , ClO 4 - , N 3 - , F - , Cl - , Br - and I - ). The duration of pre-milling and ultrasonic irradiation and the variation of synthesis temperature in the wet chemical step were investigated to obtain the optimal parameters of preparation. The main method to characterize the products was X-ray diffractometry, but infrared and synchrotron-based X-ray absorption spectroscopies as well as thermogravimetric measurements were also used to learn about fine structural details. The synthesis method afforded successful intercalation of the anions, among others the azide anion, a rarely used counter ion providing a system, which enables safe handling the otherwise highly reactive anion. The X-ray absorption spectroscopic measurements revealed that the quality of the interlayered anions could modulate the spatial arrangement of the calcium ions around the iron(III) ions, but only in the second coordination sphere. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation of polypropylene/Mg–Al layered double hydroxides nanocomposites through wet pan-milling: non-isothermal crystallization behaviour

PubMed Central

Zheng, Yilei

2018-01-01

Differential scanning calorimeter was used to extensively investigate the non-isothermal crystallization of polypropylene (PP)/layered double hydroxides (LDHs) nanocomposites prepared through wet solid-state shear milling. The corresponding crystallization kinetics was further investigated by using Ozawa, modified Avrami and combined Avrami–Ozawa method, respectively. The results showed that the Ozawa method could not well describe the crystallization kinetics of pure PP and its nanocomposites. Comparatively, the modified Avrami method as well as the combined Avrami–Ozawa method gives the satisfactory results. Under the effect of pan-milling, the produced LDH nano intercalated/exfoliated particles exhibit the inhibitive effect on the PP nucleation but more remarkable promotion effect on the spherulite growth, leading to enhancement in the overall crystallization rate. This is reflected in increase of the calculated fold surface free energy σe and also the supercooling degree ΔT required for crystallization nucleation. In addition, the polarized optical microscopy observation also verifies the higher spherulite growth rate of PP/LDHs nanocomposites than that of pure PP. PMID:29410819

New multifunctional materials obtained by the intercalation of anionic dyes into layered zinc hydroxide nitrate followed by dispersion into poly(vinyl alcohol) (PVA).

PubMed

Marangoni, Rafael; Ramos, Luiz Pereira; Wypych, Fernando

2009-02-15

Different anionic blue and orange dyes have been immobilized on a zinc hydroxide nitrate (Zn(5)(OH)(8)(NO(3))(2)nH(2)O--Zn-OH-NO(3)) by anion exchange with interlayer and/or outer surface nitrate ions of the layered matrix. Orange G (OG) was totally intercalated, orange II (OII) was partially intercalated, while Niagara blue 3B (NB) and Evans blue (EV) were only adsorbed at the outer surface. Several composite films of poly(vinyl alcohol)--PVA were prepared by casting through the dispersion of the hybrid material (Zn-OH-OG) into a PVA aqueous solution and evaporation of water in a vacuum oven. The obtained composite films were transparent, colored, and capable of absorbing UV radiation. Improved mechanical properties were also obtained in relation to the nonfilled PVA films. These results demonstrate the onset of a new range of potential applications for layered hydroxide salts in the preparation of polymer composite multifunctional materials.

Intercalation of amino acids and oligopeptides into Zn Al layered double hydroxide by coprecipitation reaction

NASA Astrophysics Data System (ADS)

Aisawa, Sumio; Sasaki, Shuji; Takahashi, Satoshi; Hirahara, Hidetoshi; Nakayama, Hirokazu; Narita, Eiichi

2006-05-01

The coprecipitation of amino acids and oligopeptides with the Zn Al LDH was investigated using phenylalanine (Phe), phenylalanyl-phenylalanine (Phe-Phe), glycyl-phenylalanine (Gly Phe), glycine (Gly), glycyl-glycine (Gly Gly), glycyl-glycyl-glycine (Gly Gly Gly) and N-(N-γ-glutamyl-cysteinyl)-glycine (GSH) as guest species. The coprecipitation behavior of amino acids and oligopeptides was found to be influenced by the solution pH and the kind of their side chain groups, and reached the maximum at pH 8 or 9. The basal spacing, d003, of the Phe, Phe-Phe and GSH/LDH was 1.81, 2.41 and 1.64 nm, supporting that guests were arranged vertical to the LDH basal layer. Acceding to the basal spacing of the Gly, Gly Gly and Gly Gly Gly/LDH (d003=0.84 0.88 nm), these guests were oriented horizontal to the LDH basal layer with the co-intercalated NO3-. Moreover, the amount of Phe-Phe, Gly Gly and Gly Gly Gly intercalated was almost the same as that of Phe and Gly despite increasing the number peptide bond and the molecular size. GSH was intercalated into the LDH interlayer space as GSH oxidized form with bridged LDH layers by their carboxylate groups.

Synthesis and properties of mecoprop-intercalated layered double hydroxide

NASA Astrophysics Data System (ADS)

Ahmed Khan, Modabber; Choi, Choong-Lyeal; Lee, Dong-Hoon; Park, Man; Lim, Bu-Kug; Lee, Jong-Yoon; Choi, Jyung

2007-08-01

This study carried out to elucidate the synthesis of MCPP LDH hybrid, release pattern of MCPP from MCPP LDH hybrid and their properties. MCPP LDH hybrid was synthesized from MCPP and Mg Al complex. Release pattern of MCPP from MCPP LDH hybrid was slower in distilled water and soil solution but it was slower in distilled water than soil solution. MCPP LDH hybrid has shown more stable condition than CO32- form of LDH in thermal and acidic condition. Therefore, MCPP LDH hybrid would lead as functional and benign pesticide to minimize the harmful effects on soil environment by bulk herbicides.

Hybridization of the natural antibiotic, cinnamic acid, with layered double hydroxides (LDH) as green pesticide.

PubMed

Park, Man; Lee, Chang-Il; Seo, Young Jin; Woo, Sang Ryung; Shin, Dongill; Choi, Jyung

2010-01-01

Heavy application of highly toxic synthetic pesticides has been committed to protect crops against insects and diseases, which have brought about serious environmental problems. Thus, an inevitable and fundamental issue has been how to protect crops without harmful effects on nature. As a fascinating nature-compatible approach, we have attempted to hybridize soil-compatible layered double hydroxides (LDHs) with natural antibiotic substances. Only a few of natural antibiotic substances are available for pest control mainly because of their inherent properties such as easy degradability, high minimum inhibition concentration for practical application, and often extremely low availability, whereas LDHs exhibit unique properties such as anion exchange capacity, acid lability, and high affinity to ubiquitous carbonate ion which make them an excellent inorganic matrix to carry labile biomolecules in soils. This study focuses on the behavior of cinnamate-LDH hybrid in soils and the evaluation of its potentials as a green pesticide. The cinnamate-LDH hybrid was synthesized by a typical coprecipitation method. Cinnamic acid was analyzed by high performance liquid chromatography which was operated at 280 nm with C18 column. Its controlled release property was evaluated in a cultivated soil as well as a simulated soil solution. Its antifungal activity was examined against the growth of Phytophyhora capsici in a potato dextrose agar medium and a red pepper seedling, respectively. Structural characterization by X-ray diffraction, infra-red, and thermal analysis indicates that cinnamate molecules are safely intercalated into the interlayer space of inorganic layers of LDH by the electrostatic interaction to have an empirical formula of Mg(3)Al(OH)(8).CAN . 3.1H(2)O. The overall release pattern of the intercalated cinnamate in the soil solution could be best described by the power-function equation [Formula: see text]. This suggests that diffusion-controlled processes besides simple ion-exchange process play an important role in release of the intercalated cinnamate. Furthermore, its behavior in a cultivated soil clearly shows that hybridization leads to protection of cinnamate against the degradation as well as to a controlled release in soils. Its antifungal activity against the growth of P. capsici in a potato dextrose agar medium and a red pepper seedling definitely shows that the hybrid is very effective in controlling the root rot of red pepper. This study demonstrates that the hybridization of natural antibiotic substances with layered double hydroxides could be a fascinating alternative for green formulation of pesticides. This unique hybrid system leads to the salient features such as protection of the substances against chemical and microbial degradations, controlled release, and nature compatibility. This study suggests one of the sound strategies to make a breakthrough in the formulation of green pesticides. Hybridization with inorganic matrixes not only enables the natural antibiotic substances to replace the synthetic ingredients but also adjuvants to be excluded from the formulations. Furthermore, the resulting hybrid exhibits a controlled release of the intercalated substances. Although substantiated further, this study is expected to attract a great deal of attention to reliable application of natural antibiotic substances in green protection of crops and agricultural products.

Intercalation of p-methycinnamic acid anion into Zn-Al layered double hydroxide to improve UV aging resistance of asphalt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Chao; State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070; Dai, Jing

2015-02-15

A UV absorber, p-methycinnamic acid (PMCA), was intercalated into Zn-Al layered double hydroxide (LDH) by calcination recovery. Fourier transform infrared spectroscopy showed that the PMCA anions completely replaced the CO{sub 3}{sup 2−} anions in the interlayer galleries of Zn-Al-LDH containing PMCA anions (Zn-Al-PMCA-LDH). X-ray diffraction and transmission electron microscopy showed that the interlayer distance increased from 0.78 nm to 1.82 nm after the substitution of PMCA anions for CO{sub 3}{sup 2−} anions. The similar diffraction angles of the CO{sub 3}{sup 2−} anion-containing Zn-Al-LDH (Zn-Al-CO{sub 3}{sup 2−}-LDH) and the Zn-Al-CO{sub 3}{sup 2−}-LDH/styrene–butadiene–styrene (SBS) modified asphalt implied that the asphalt molecules domore » not enter into the LDH interlayer galleries to form separated-phase structures. The different diffraction angles of Zn-Al-PMCA-LDH and Zn-Al-PMCA-LDH/SBS modified asphalt indicated that the asphalt molecules penetrated into the LDH interlayer galleries to form an expanded-phase structure. UV-Vis absorbance analyses showed that Zn-Al-PMCA-LDH was better able to block UV light due to the synergistic effects of PMCA and Zn-Al-LDH. Conventional physical tests and atomic force microscopy images of the SBS modified asphalt, Zn-Al-CO{sub 3}{sup 2−}-LDH/SBS modified asphalt and Zn-Al-PMCA-LDH/SBS modified asphalt before and after UV aging indicated that Zn-Al-PMCA-LDH improved the UV aging resistance of SBS modified asphalts.« less

Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine

NASA Astrophysics Data System (ADS)

Li, Meixia; Zhu, Jun E.; Zhang, Lili; Chen, Xu; Zhang, Huimin; Zhang, Fazhi; Xu, Sailong; Evans, David G.

2011-10-01

Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach.Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach. Electronic supplementary information (ESI) available: Fig. S1 showing 2D fast Fourier transform (FFT) image of NiAl-LDH phase in NiAl-LDH/G composites, and Fig. S2 showing CV curve of the pristine G modified electrode. See DOI: 10.1039/c1nr10592b.

Antifouling composites with self-adaptive controlled release based on an active compound intercalated into layered double hydroxides

NASA Astrophysics Data System (ADS)

Yang, Miaosen; Gu, Lianghua; Yang, Bin; Wang, Li; Sun, Zhiyong; Zheng, Jiyong; Zhang, Jinwei; Hou, Jian; Lin, Cunguo

2017-12-01

This paper reports a novel method to prepare the antifouling composites with properties of self-adaptive controlled release (defined as control the release rate autonomously and adaptively according to the change of environmental conditions) by intercalation of sodium paeonolsilate (PAS) into MgAl and ZnAl layered double hydroxide (LDH) with the molar ratio (M2+/M3+) of 2:1 and 3:1, respectively. The powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) confirm the intercalation of PAS into the galleries of LDH. The controlled release behavior triggered by temperature for the PAS-LDH composites has been investigated, and the results show that the release rate of all PAS-LDH composites increases as the increase of temperature. However, the MgAl-PAS-LDH composites (Mg2Al-PAS-LDH and Mg3Al-PAS-LDH) exhibit the increased release rate of 0.21 ppm/°C from 15 to 30 °C in 3.5% NaCl solution, more than three times of the ZnAl-PAS-LDH composites (0.06 ppm/°C), owing to the confined microenvironment influenced by metal types in LDH layers. In addition, a possible diffusion-controlled process with surface diffusion, bulk diffusion and heterogeneous flat surface diffusion has been revealed via fitting four kinetic equations. Moreover, to verify the practical application of the PAS-LDH composites, a model coating denoted as Mg2Al-PAS-LDH coating was fabricated. The release result displays that the release rate increases or decreases as temperature altered at 15 and 25 °C alternately, indicating its self-adaptive controlled release behavior with temperature. Moreover, the superior resistance to the settlement of Ulva spores at 15 and 25 °C was observed for the Mg2Al-PAS-LDH coating, as a result of the controllable release of antifoulant. Therefore, this work provides a facile and effective method for the fabrication of antifouling composites with self-adaptive controlled release behavior in response to temperature, which can be used to prolong the lifetime of antifouling coatings.

Highly Selective and Efficient Removal of Heavy Metals by Layered Double Hydroxide Intercalated with the MoS4(2-) Ion.

PubMed

Ma, Lijiao; Wang, Qing; Islam, Saiful M; Liu, Yingchun; Ma, Shulan; Kanatzidis, Mercouri G

2016-03-02

The MoS4(2-) ion was intercalated into magnesium-aluminum layered double hydroxide (MgAl-NO3-LDH) to produce a single phase material of Mg0.66Al0.34(OH)2(MoS4)0.17·nH2O (MgAl-MoS4-LDH), which demonstrates highly selective binding and extremely efficient removal of heavy metal ions such as Cu(2+), Pb(2+), Ag(+), and Hg(2+). The MoS4-LDH displays a selectivity order of Co(2+), Ni(2+), Zn(2+) < Cd(2+) ≪ Pb(2+) < Cu(2+) < Hg(2+) < Ag(+) for the metal ions. The enormous capacities for Hg(2+) (∼500 mg/g) and Ag(+) (450 mg/g) and very high distribution coefficients (Kd) of ∼10(7) mL/g place the MoS4-LDH at the top of materials known for such removal. Sorption isotherm for Ag(+) agrees with the Langmuir model suggesting a monolayer adsorption. It can rapidly lower the concentrations of Cu(2+), Pb(2+), Hg(2+), and Ag(+) from ppm levels to trace levels of ≤1 ppb. For the highly toxic Hg(2+) (at ∼30 ppm concentration), the adsorption is exceptionally rapid and highly selective, showing a 97.3% removal within 5 min, 99.7% removal within 30 min, and ∼100% removal within 1 h. The sorption kinetics for Cu(2+), Ag(+), Pb(2+), and Hg(2+) follows a pseudo-second-order model suggesting a chemisorption with the adsorption mechanism via M-S bonding. X-ray diffraction patterns of the samples after adsorption demonstrate the coordination and intercalation structures depending on the metal ions and their concentration. After the capture of heavy metals, the crystallites of the MoS4-LDH material retain the original hexagonal prismatic shape and are stable at pH ≈ 2-10. The MoS4-LDH material is thus promising for the remediation of heavy metal polluted water.

Thermodynamical and structural insights of orange II adsorption by Mg{sub R}AlNO{sub 3} layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mustapha Bouhent, Mohamed; Laboratoire des Materiaux Inorganiques, UMR CNRS 6002, Universite Blaise Pascal, F-63177 Aubiere Cedex; Derriche, Zoubir, E-mail: derriche_zoubir@yahoo.co

2011-05-15

[Mg{sub 1-x} Al{sub x}(OH){sub 2}][(NO{sub 3}){sub x}, nH{sub 2}O] Layered Double Hydroxide (LDH) sorbents with variable Mg/Al molar (R=(1-x)/x) ratios were investigated for adsorption of azo dye, orange II (OII) at various pH and temperature conditions. Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. Adsorption isotherms have been fitted using the Langmuir model and free energy of adsorption ({Delta}G{sup o}), enthalpy ({Delta}H{sup o}) and entropy ({Delta}S{sup o}) were calculated. The experimental values for {Delta}G{sup o} in temperature range between 10 and 40 {sup o}C weremore » found to be negative indicating that a spontaneous process occurred. Positive calculated enthalpy values, characteristic of an endothermic process were found. Characterization of solids (PXRD, FTIR, UV-vis, TGA/DTA, adsorption isotherm BET analysis, SEM and Zetametry) before and after adsorption showed that adsorption proceeds in two steps. First, adsorption occurs at the LDH surface, followed by intercalation via anion exchange. -- Graphical Abstract: Structural and thermodynamical insight of adsorption/Intercalation of OII in Mg{sub R}Al LDH Display Omitted Highlights: {yields} The nitrate containing hydrotalcite-like compounds (Mg{sub R}AlNO{sub 3} LDH) were prepared by the coprecipitation method. {yields} Adsorption of anionic orange dye(OII) is studied on LDHs at different temperatures. {yields} The adsorption process is well described by the Langmuir isotherm model. {yields} Mg{sub 2}AlNO{sub 3} displays the highest adsorption capacity with 3.611 mmol of OII per gram of Mg{sub 2}AlNO{sub 3} at 40 {sup o}C. {yields} Adsorption process does not occur on the surface of the LDH only but an intercalation process is also occurring concomitantly according to the thermodynamical values.« less

New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

PubMed

Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

2015-08-15

Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal. Copyright © 2015 Elsevier B.V. All rights reserved.

Anionic clay as the drug delivery vehicle: tumor targeting function of layered double hydroxide-methotrexate nanohybrid in C33A orthotopic cervical cancer model

PubMed Central

Choi, Goeun; Piao, Huiyan; Alothman, Zeid A; Vinu, Ajayan; Yun, Chae-Ok; Choy, Jin-Ho

2016-01-01

Methotrexate (MTX), an anticancer agent, was successfully intercalated into the anionic clay, layered double hydroxides to form a new nanohybrid drug. The coprecipitation and subsequent hydrothermal method were used to prepare chemically, structurally, and morphologically well-defined two-dimensional drug-clay nanohybrid. The resulting two-dimensional drug-clay nanohybrid showed excellent colloidal stability not only in deionized water but also in an electrolyte solution of Dulbecco’s Modified Eagle’s Medium with 10% fetal bovine serum, in which the average particle size in colloid and the polydispersity index were determined to be around 100 and 0.250 nm, respectively. The targeting property of the nanohybrid drug was confirmed by evaluating the tumor-to-blood and tumor-to-liver ratios of the MTX with anionic clay carrier, and these ratios were compared to those of free MTX in the C33A orthotopic cervical cancer model. The biodistribution studies indicated that the mice treated with the former showed 3.5-fold higher tumor-to-liver ratio and fivefold higher tumor-to-blood ratio of MTX than those treated with the latter at 30 minutes postinjection. PMID:26855572

Anionic clay as the drug delivery vehicle: tumor targeting function of layered double hydroxide-methotrexate nanohybrid in C33A orthotopic cervical cancer model.

PubMed

Choi, Goeun; Piao, Huiyan; Alothman, Zeid A; Vinu, Ajayan; Yun, Chae-Ok; Choy, Jin-Ho

2016-01-01

Methotrexate (MTX), an anticancer agent, was successfully intercalated into the anionic clay, layered double hydroxides to form a new nanohybrid drug. The coprecipitation and subsequent hydrothermal method were used to prepare chemically, structurally, and morphologically well-defined two-dimensional drug-clay nanohybrid. The resulting two-dimensional drug-clay nanohybrid showed excellent colloidal stability not only in deionized water but also in an electrolyte solution of Dulbecco's Modified Eagle's Medium with 10% fetal bovine serum, in which the average particle size in colloid and the polydispersity index were determined to be around 100 and 0.250 nm, respectively. The targeting property of the nanohybrid drug was confirmed by evaluating the tumor-to-blood and tumor-to-liver ratios of the MTX with anionic clay carrier, and these ratios were compared to those of free MTX in the C33A orthotopic cervical cancer model. The biodistribution studies indicated that the mice treated with the former showed 3.5-fold higher tumor-to-liver ratio and fivefold higher tumor-to-blood ratio of MTX than those treated with the latter at 30 minutes postinjection.

Layered zinc hydroxide salts: delamination, preferred orientation of hydroxide lamellae, and formation of ZnO nanodiscs.

PubMed

Demel, Jan; Pleštil, Josef; Bezdička, Petr; Janda, Pavel; Klementová, Mariana; Lang, Kamil

2011-08-15

Delamination of layered zinc hydroxide salts (LZH) into hydroxide layers provides nanobuilding blocs of a two-dimensional anisotropy. The methodology, extent of delamination, the size and stability of hydroxide lamellae are described in detail. The ability of lamellae to restack to form oriented hydroxide films depends on the solvent, original LZH salt, and conditions used for delamination. The most interesting results were obtained using LZH intercalated with dodecyl sulfate anions and LZH nitrate delaminated in butanol at 60 °C and in formamide at room temperature, respectively. The former method produces hydroxide lamellae of a lateral size of ca. 10-20 nm. The inner structure of the hydroxide layers is conserved and separated lamellae restack to the original layered structure of LZH dodecyl sulfate. The latter method yields lamellae with a size decreasing from 73.3 nm to 10 nm after a 2-week aging, while their thickness is nearly constant (2.6-3.8 nm). However, the use of formamide is complicated by the formation of Zn(II) formate. The major part of LZH intercalated with dodecyl sulfate anions is transformed during the delamination procedure to anisotropic ZnO nanoparticles, either needle-like particles prolonged in the [0 0 1] direction or disc-like particles flattened along the (0 0 1) plane. Copyright © 2011 Elsevier Inc. All rights reserved.

Preparation and characterization of an anti-inflammatory agent based on a zinc-layered hydroxide-salicylate nanohybrid and its effect on viability of Vero-3 cells

PubMed Central

Ramli, Munirah; Hussein, Mohd Zobir; Yusoff, Khatijah

2013-01-01

A new organic-inorganic nanohybrid based on zinc-layered hydroxide intercalated with an anti-inflammatory agent was synthesized through direct reaction of salicylic acid at various concentrations with commercially available zinc oxide. The basal spacing of the pure phase nanohybrid was 15.73 Å, with the salicylate anions arranged in a monolayer form and an angle of 57 degrees between the zinc-layered hydroxide interlayers. Fourier transform infrared study further confirmed intercalation of salicylate into the interlayers of zinc-layered hydroxide. The loading of salicylate in the nanohybrid was estimated to be around 29.66%, and the nanohybrid exhibited the properties of a mesoporous-type material, with greatly enhanced thermal stability of the salicylate compared with its free counterpart. In vitro cytotoxicity assay revealed that free salicylic acid, pure zinc oxide, and the nanohybrid have a mild effect on viability of African green monkey kidney (Vero-3) cells. PMID:23345976

Intercalation of anionic organic ultraviolet ray absorbers into layered zinc hydroxide nitrate.

PubMed

Cursino, Ana Cristina Trindade; Gardolinski, José Eduardo Ferreira da Costa; Wypych, Fernando

2010-07-01

Layered zinc hydroxide nitrate (ZHN) was synthesized and nitrate ions were topotactically exchanged with three different anionic species of commercial organic ultraviolet (UV) ray absorbers: 2-mercaptobenzoic acid, 2-aminobenzoic acid, and 4-aminobenzoic acid. The exchange reactions were confirmed by X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR), ultraviolet visible (UV-Vis) spectroscopy, and thermal analysis (thermogravimetry, TGA, and differential thermal analysis, DTA). In all the anionic exchanged products, evidence of grafting of the organic species onto the inorganic matrix was obtained. In general, after intercalation/grafting, the UV absorption ability was improved in relation to the use of the parent organic material, showing that layered hydroxide salts (LHS) can be good alternative matrixes for the immobilization of organic species with UV-blocking properties in cosmetic products. Copyright 2010 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia Shengjie; Ni Zheming; Xu Qian

Zn/Al layered double hydroxides (LDHs) were intercalated with the anionic antihypertensive drugs Enalpril, Lisinopril, Captopril and Ramipril by using coprecipitation or ion-exchange technique. TG-MS analyses suggested that the thermal stability of Ena{sup -}, Lis{sup -} (arranged with monolayer, resulted from X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) analysis was enhanced much more than Cap{sup -} and Ram{sup -} (arranged with bilayer). The release studies show that the release rate of all samples markedly decreased in both pH 4.25 and 7.45. However, the release time of Ena{sup -}, Lis{sup -} were much longer compared with Cap{sup -}, Ram{sup -}more » in both pH 4.25 and 7.45, it is possible that the intercalated guests, arranged with monolayer in the interlayer, show lesser repulsive force and strong affinity with the LDH layers. And the release data followed both the Higuchi-square-root law and the first-order equation well. Based on the analysis of batch release, intercalated structural models as well as the TG-DTA results, we conclude that for drug-LDH, stronger the affinity between intercalated anions and the layers is, better the thermal property and the stability to the acid attack of drug-LDH, and the intercalated anions are easier apt to monolayer arrangement within the interlayer, were presented. - Graphical abstract: A series of antihypertensive drugs including Enalpril, Lisinopril, Captopril and Ramipril were intercalated into Zn/Al-NO{sub 3}-LDHs successfully by coprecipitation or ion-exchange technique. We focus on the structure, thermal property and low/controlled release property of as-synthesized drug-LDH composite intended for the possibility of applying these LDH-antihypertensive nanohybrids in drug delivery and controlled release systems.« less

Preparation and Characterization of Polyhydroxybutyrate/Polycaprolactone Nanocomposites

PubMed Central

Liau, Cha Ping; Bin Ahmad, Mansor; Shameli, Kamyar; Yunus, Wan Md Zin Wan

2014-01-01

Polyhydroxybutyrate (PHB)/polycaprolactone (PCL)/stearate Mg-Al layered double hydroxide (LDH) nanocomposites were prepared via solution casting intercalation method. Coprecipitation method was used to prepare the anionic clay Mg-Al LDH from nitrate salt solution. Modification of nitrate anions by stearate anions between the LDH layers via ion exchange reaction. FTIR spectra showed the presence of carboxylic acid (COOH) group which indicates that stearate anions were successfully intercalated into the Mg-Al LDH. The formation of nanocomposites only involves physical interaction as there are no new functional groups or new bonding formed. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the mixtures of nanocomposites are intercalated and exfoliated types. XRD results showed increasing of basal spacing from 8.66 to 32.97 Å in modified stearate Mg-Al LDH, and TEM results revealed that the stearate Mg-Al LDH layers are homogeneously distributed in the PHB/PCL polymer blends matrix. Enhancement in 300% elongation at break and 66% tensile strength in the presence of 1.0 wt % of the stearate Mg-Al LDH as compare with PHB/PCL blends. Scanning electron microscopy (SEM) proved that clay improves compatibility between polymer matrix and the best ratio 80PHB/20PCL/1stearate Mg-Al LDH surface is well dispersed and stretched before it breaks. PMID:24600329

Orthogonal test design for optimization of synthesis of MTX/LDHs hybrids by ion-exchange method

NASA Astrophysics Data System (ADS)

Liu, Su-Qing; Dai, Chao-Fan; Wang, Lin; Li, Shu-Ping; Li, Xiao-Dong

2015-04-01

Based on orthogonal test design, the factors influencing the synthesis of methotrexate intercalated magnesium-aluminum layered double hydroxides (MTX/LDHs for short) by ion-exchange method, such as weight ratio of pristine LDHs to MTX (R for short), exchange temperature, time and pH value were investigated. Of the four controllable independent variables, R had the strongest effect on the crystallinity and the drug-loading capacity and the optimum synthesis conditions considered from the crystallinity and the drug-loading capacity both pointed to the same values, i.e., R=2:1, pH=9.5, temperature of 80 °C and exchange time of 3 day. The XRD diffractions indicated that high MTX content was in favor of the formation of intercalated hybrids, while low content lead to the failure of it. TEM photos indicated that the intercalated hybrids all exhibited aggregated hexagonal plates. In order to improve the morphology, two different states of pristine LDHs, i.e., powder and colloid, were chosen to prepare MTX/LDHs hybrids and the results indicated that colloid state of pristine was advantageous to obtain regular particles. The study also revealed that the properties of hybrids obtained at optimum conditions by ion-exchange were superior to that obtained from standard methods, such as co-precipitation method.

Recent Advances in Solid Catalysts Obtained by Metalloporphyrins Immobilization on Layered Anionic Exchangers: A Short Review and Some New Catalytic Results.

PubMed

Nakagaki, Shirley; Mantovani, Karen Mary; Machado, Guilherme Sippel; Castro, Kelly Aparecida Dias de Freitas; Wypych, Fernando

2016-02-29

Layered materials are a very interesting class of compounds obtained by stacking of two-dimensional layers along the basal axis. A remarkable property of these materials is their capacity to interact with a variety of chemical species, irrespective of their charge (neutral, cationic or anionic). These species can be grafted onto the surface of the layered materials or intercalated between the layers, to expand or contract the interlayer distance. Metalloporphyrins, which are typically soluble oxidation catalysts, are examples of molecules that can interact with layered materials. This work presents a short review of the studies involving metalloporphyrin immobilization on two different anionic exchangers, Layered Double Hydroxides (LDHs) and Layered Hydroxide Salts (LHSs), published over the past year. After immobilization of anionic porphyrins, the resulting solids behave as reusable catalysts for heterogeneous oxidation processes. Although a large number of publications involving metalloporphyrin immobilization on LDHs exist, only a few papers have dealt with LHSs as supports, so metalloporphyrins immobilized on LHSs represent a new and promising research field. This work also describes new results on an anionic manganese porphyrin (MnP) immobilized on Mg/Al-LDH solids with different nominal Mg/Al molar ratios (2:1, 3:1 and 4:1) and intercalated with different anions (CO₃(2-) or NO₃(-)). The influence of the support composition on the MnP immobilization rates and the catalytic performance of the resulting solid in cyclooctene oxidation reactions will be reported.

Layered Double Hydroxide Minerals as Possible Prebiotic Information Storage and Transfer Compounds

NASA Astrophysics Data System (ADS)

Greenwell, H. Chris; Coveney, Peter V.

2006-02-01

One of the fundamental difficulties when considering the origin of life on Earth is the identification of an emergent system that not only replicated, but also had the capacity to undergo discrete mutation in such a way that following generations might inherit and pass on the mutation. We speculate that the layered double hydroxide (LDH) minerals are plausible candidates for a proto-RNA molecule. We describe a hypothetical LDH-like system which, when intercalated with certain anions, forms crystals with a high degree of internal order giving rise to novel information storage structures in which replication fidelity is maintained, a concept we use to propose an explanation for interstratification in terephthalate LDHs. The external surfaces of these hypothetical crystals provide active sites whose structure and chemistry is dictated by the internal information content of the LDH. Depending on the LDH polytype, the opposing external surfaces of a crystal may give rise to reactive sites that are either complementary or mirror images of each other, and so may be chiral. We also examine similarities between these proposed “proto-RNA” structures and the DNA that encodes the hereditary information in life today, concluding with a hypothetical scenario wherein these proto-RNA molecules predated the putative RNA-world.

Antituberculosis nanodelivery system with controlled-release properties based on para-amino salicylate–zinc aluminum-layered double-hydroxide nanocomposites

PubMed Central

Saifullah, Bullo; Hussein, Mohd Zobir; Hussein-Al-Ali, Samer Hasan; Arulselvan, Palanisamy; Fakurazi, Sharida

2013-01-01

We report the intercalation and characterization of para-amino salicylic acid (PASA) into zinc/aluminum-layered double hydroxides (ZLDHs) by two methods, direct and indirect, to form nanocomposites: PASA nanocomposite prepared by a direct method (PASA-D) and PASA nanocomposite prepared by an indirect method (PASA-I). Powder X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis revealed that the PASA drugs were accommodated within the ZLDH interlayers. The anions of the drug were accommodated as an alternate monolayer (along the long-axis orientation) between ZLDH interlayers. Drug loading was estimated to be 22.8% and 16.6% for PASA-D and PASA-I, respectively. The in vitro release properties of the drug were investigated in physiological simulated phosphate-buffered saline solution of pH 7.4 and 4.8. The release followed the pseudo-second-order model for both nanocomposites. Cell viability (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide [MTT] assays) was assessed against normal human lung fibroblast MRC-5 and 3T3 mouse fibroblast cells at 24, 48, and 72 hours. The results showed that the nanocomposite formulations did not possess any cytotoxicity, at least up to 72 hours. PMID:24255593

Enhanced fluoride removal by La-doped Li/Al layered double hydroxides.

PubMed

Cai, Jianguo; Zhao, Xin; Zhang, Yanyang; Zhang, Quanxing; Pan, Bingcai

2018-01-01

In this study La intercalated Li/Al layered double hydroxide (LDH) was developed for efficient water defluoridation. The La-modified material, i.e., La doped Li/Al-LDH, exhibits more preferable fluoride adsorption than Li/Al-LDH in a broad pH range of 5-9, with the working capacity twice of the latter and seven times of magnitude higher than activated alumina. The fluoride removal kinetics is well fitted by pseudo-second order model, and the adsorption isotherm is well described by Freundlich model. Effect of pH and competing ions was examined during fluoride sequestration. The underlying mechanism for such enhanced adsorption of fluoride by La doped Li/Al-LDH was further revealed based on XPS and FTIR analysis. The presence of La and Al was found to be responsible for the satisfactory defluoridation of La doped Li/Al-LDH, and chloride replacement with fluoride occurred from both LDHs during fluoride adsorption. Also, the capacity of La doped Li/Al-LDH could be refreshed by alkaline solution (pH = 12) for cyclic runs. All the results implied that La doped Li/Al-LDH could serve asa potential adsorbent for efficient fluoride removal from water. Copyright © 2017 Elsevier Inc. All rights reserved.

Stabilization of antioxidant gallate in layered double hydroxide by exfoliation and reassembling reaction

NASA Astrophysics Data System (ADS)

Ansy, Kanakappan Mickel; Lee, Ji-Hee; Piao, Huiyan; Choi, Goeun; Choy, Jin-Ho

2018-06-01

As for the stabilization of chemically sensitive bioactive molecule in this study, gallic acid (GA) with antioxidant property was intercalated into interlayer space of layered double hydroxide (LDH), which was realized by exfoliation and reassembling reaction. At first, the pristine nitrate-type Zn2Al-LDH in solid state was synthesized via co-precipitation followed by the hydrothermal treatment at 80 °C for 6 h, and then exfoliated in formamide to form a colloidal solution of exfoliated LDH nanosheets, and finally reassembled in the presence of GA to prepare GA intercalated LDH (GA-LDH) desired, where the pH was adjusted to 8.0 in order to deprotonate GA to form gallate anion. According to the XRD analysis, GA-LDH showed well-developed (00l) diffraction peaks with a basal spacing of 1.15 nm, which was estimated to be larger than that of the pristine LDH (0.88 nm), indicating that gallate molecules were incorporated into LDH layers with perpendicular orientation. From the FT-IR spectra it was found that gallic acid was completely deprotonated into gallate, and stabilized in between LDH lattices via electrostatic interaction. The content of GA in GA-LDH was determined to be around 23 wt% by UV-vis spectroscopic study, which was also confirmed by HPLC analysis. According to the in-vitro release of GA out of GA-LDH in PBS solution (pH 7.4) at 4 °C, GA was sustainably released from GA-LDH nanohybrid up to 86% within 72 h. The antioxidant property of GA-LDH was almost the same with that of intact GA which was examined by DPPH. The photostability of GA-LDH under UV light irradiation was immensely enhanced compared to intact GA. It is, therefore, concluded that the present GA-LDH nanohybrid can be considered as an excellent antioxidant material with high chemical- and photo-stabilities, and controlled release property.

Pectins filled with LDH-antimicrobial molecules: preparation, characterization and physical properties.

PubMed

Gorrasi, Giuliana; Bugatti, Valeria; Vittoria, Vittoria

2012-06-05

Nanohybrids of layered double hydroxide (LDH) with intercalated active molecules: benzoate, 2,4-dichlorobenzoate, para-hydroxybenzoate and ortho-hydroxybenzoate, were incorporated into pectins from apples through high energy ball milling in the presence of water. Cast films were obtained and analysed. X-ray diffraction analysis showed a complete destructuration of all nanohybrids in the pectin matrix. Thermogravimetric analysis showed a better thermal resistance of pectin in the presence of fillers, especially para-hydroxybenzoate and ortho-hydroxybenzoate. Mechanical properties showed an improvement of elastic modulus in particular for LDH-para-hydroxybenzoate nanohybrid, due probably to a better interaction between pectin matrix and nanohybrid layers. Barrier properties (sorption and diffusion) to water vapour showed improvement in the dependence on the intercalated active molecule, the best improvement was achieved for composites containing para-hydroxybenzoate molecules, suggesting that the interaction between the filler phase and the polymer plays an important role in sorption and diffusion phenomena. Incorporation of these active molecules gave antimicrobial properties to the composite films giving opportunities in the field of active packaging. Copyright © 2012 Elsevier Ltd. All rights reserved.

Magnetic ordering of nickel hydroxide layers 30 Å apart obtained by intercalating dodecyl sulfate

NASA Astrophysics Data System (ADS)

Seehra, M. S.; Singh, V.

2013-09-01

The nature of magnetic ordering in quasi-2D layered hydroxide of Ni (LH-Ni-DS) with hexagonal structure and synthesized by intercalating dodecyl sulfate (DS) ligand, (C12H25OSO3)-, between the layers using a hydrothermal technique is investigated. The observation of (00l) peaks up to l = 8 in x-ray diffraction on the sample yields an interlayer spacing c ≃ 30.5 Å and a crystallite size ≃ 16 nm. Assignment of the lines observed in the FTIR spectra to the various groups of the DS ligand confirms the intercalation. From the analysis of detailed investigations of the temperature dependence of the magnetization M at different magnetic fields, ac susceptibilities at frequencies from 0.1 to 1 kHz, and electron magnetic resonance spectra at 9.28 GHz, it is concluded that LH-Ni-DS orders ferromagnetically at TC ≃ 23 K. This TC is about 45% higher than TC ≃ 16 K reported for LH-Ni-Ac with c ≃ 8.6 Å obtained by intercalating an acetate ligand between the layers. The roles of the interlayer dipolar interaction, magnetic anisotropy and exchange interactions in determining TC in LH-Ni-L systems for several ligands L yielding different c-axes are discussed.

Enhanced anti-inflammatory potential of cinnamate-zinc layered hydroxide in lipopolysaccharide-stimulated RAW 264.7 macrophages

PubMed Central

Adewoyin, Malik; Mohsin, Sumaiyah Megat Nabil; Arulselvan, Palanisamy; Hussein, Mohd Zobir; Fakurazi, Sharida

2015-01-01

Background Cinnamic acid (CA) is a phytochemical originally derived from Cinnamomum cassia, a plant with numerous pharmacological properties. The intercalation of CA with a nanocarrier, zinc layered hydroxide, produces cinnamate-zinc layered hydroxide (ZCA), which has been previously characterized. Intercalation is expected to improve the solubility and cell specificity of CA. The nanocarrier will also protect CA from degradation and sustain its release. The aim of this study was to assess the effect of intercalation on the anti-inflammatory capacity of CA. Methods In this study, the anti-inflammatory activity of ZCA was investigated and compared with that of nonintercalated CA. Evaluations were based on the capacity of ZCA and CA to modulate the release of nitric oxide, prostaglandin E2, interleukin (IL)-6, tumor necrosis factor alpha (TNF-α), IL-1β, and IL-10 in lipopolysaccharide-induced RAW 264.7 cells. Additionally, the expression of proinflammatory enzymes, ie, cyclooxygenase-2, inducible nitric oxide synthase, and nuclear factor kappa B (NF-κB), were examined. Results Although both ZCA and CA downregulated nitric oxide, prostaglandin E2, tumor necrosis factor alpha, IL-1β, and IL-6, ZCA clearly displayed better activity. Similarly, expression of cyclooxygenase-2 and inducible nitric oxide synthase were inhibited in samples treated with ZCA and CA. The two compounds effectively inactivated the transcription factor NF-κB, but the anti-inflammatory cytokine, IL-10, was significantly upregulated by ZCA only. Conclusion The present findings suggest that ZCA possesses better anti-inflammatory potential than CA, while zinc layered hydroxide had little or no effect, and these results were comparable with the positive control. PMID:25995619

Enhanced effects of low molecular weight heparin intercalated with layered double hydroxide nanoparticles on rat vascular smooth muscle cells.

PubMed

Gu, Zi; Rolfe, Barbara E; Xu, Zhi P; Thomas, Anita C; Campbell, Julie H; Lu, Gao Q M

2010-07-01

Surgical procedures to remove atherosclerotic lesions and restore blood flow also injure the artery wall, promoting vascular smooth muscle cell (SMC) phenotypic change, migration, proliferation, matrix production and ultimately, restenosis of the artery. Hence identification of effective anti-restenotic strategies is a high priority in cardiovascular research, and SMCs are a key target for intervention. This paper presents the in vitro study of layered double hydroxides (LDHs) as drug delivery system for an anti-restenotic drug (low molecular weight heparin, LMWH). The cytotoxicity tests showed that LDH itself had very limited toxicity at concentrations below 50 microg/mL over 6-day incubation. LDH nanoparticles loaded with LMWH (LMWH-LDHs) were prepared and tested on rat vascular SMCs. When conjugated to LDH particles, LMWH enhanced its ability to inhibit SMC proliferation and migration, with greater than above 60% reduction compared with the control (growth medium) over 3 or 7-day incubation. Cellular uptake studies showed that compared with LMWH alone, LMWH-LDH hybrids were internalized by SMCs more rapidly, and uptake was sustained over a longer time, possibly revealing the mechanisms underlying the enhanced biological function of LMWH-LDH. The results suggest the potential of LMWH-LDH as an efficient anti-restenotic drug for clinical application. Copyright 2010 Elsevier Ltd. All rights reserved.

Enhanced removal of natural organic matters by calcined Mg/Al layered double hydroxide nanocrystalline particles: Adsorption, reusability and mechanism studies

NASA Astrophysics Data System (ADS)

Fang, Liping; Hou, Jingwei; Xu, Cuihong; Wang, Yaru; Li, Ji; Xiao, Feng; Wang, Dongsheng

2018-06-01

Natural organic matters (NOMs) can generate disinfection by-products during water treatment process, threatening to human health. However, the removal of NOM is still unsatisfactory in water treatment. Hence, this work investigated the removal efficiency of humic and fulvic acids (HA and FA) by layered double hydroxide (LDH) and its calcined forms under different conditions. Our results show that calcination of LDH at 500 °C can effectively enhance the NOM removal with adsorption capacities of 98.8 mg/g for HA and 97.6 mg/g for FA at pH 9.5. The removal efficiency of HA and FA notably increases by decreasing pH. The presence of SO42- and CO32- significantly suppresses the removal of HA or FA by CLDHs. The release of Al from LDH and CLDH is negligible and safe to aquatic organisms at pH > 6.5. Moreover, CLDH shows a good reusability for NOM removal in water treatment. The removal of HA and FA by CLDH is governed through electrostatic interactions and intercalation into the interlayers of LDH was not observed. Fluorescence and molecular weight analyses show that the microbial by-products with mid-molecular weight are more difficult to be removed than HA and FA. This study provides a new insight into the NOM removal using LDH and CLDH.

Hierarchical layered double hydroxides with Ag nanoparticle modification for ethanol sensing

NASA Astrophysics Data System (ADS)

Qin, Yuxiang; Wang, Liping; Wang, Xiaofei

2018-07-01

Layered double hydroxides (LDHs) have recently been revealed to be promising in gas sensor applications due to their compositional flexibility and unique 2D-interlayer channel for gas diffusion and adsorption. This work demonstrates highly porous hierarchical LDHs containing Mg2+ and Al3+ (MgAl-LDHs) for ethanol sensing at room temperature. These MgAl-LDHs, with unique flower-like hierarchical structure and mesoporous interlayer, were synthesized hydrothermally using sodium dodecyl sulfate as soft template as well as intercalating agent. Further modification by discrete Ag nanoparticles (NPs) was achieved via an environmentally friendly glucose-reduction method to improve the gas-sensing response of the LDH-based sensor. It is found that the hierarchical MgAl-LDHs show potential in sensing ethanol gas with rapid dynamic characteristics at room temperature; their response magnitude towards ethanol can be enhanced significantly by Ag NP modification. The gas-response value of the Ag-modified MgAl-LDH sensor is about twice that of pristine MgAl-LDH sensors, towards 5–200 ppm ethanol at room temperature. Meanwhile, rapid response-recovery characteristics are achieved, with response and recovery times shorter than 10 and 50 s, respectively. The satisfactory sensing performance and remarkable response enhancement by Ag NP modification are demonstrated in terms of the unique microstructure of the hierarchical MgAl-LDHs and a constructed conductive effect model of Ag functionalized LDHs.

Large-scale fabrication of linear low density polyethylene/layered double hydroxides composite films with enhanced heat retention, thermal, mechanical, optical and water vapor barrier properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jiazhuo; Zhang, Kun; Zhao, Qinghua

Novel LDH intercalated with organic aliphatic long-chain anion was large-scale synthesized innovatively by high-energy ball milling in one pot. The linear low density polyethylene (LLDPE)/layered double hydroxides (LDH) composite films with enhanced heat retention, thermal, mechanical, optical and water vapor barrier properties were fabricated by melt blending and blowing process. FT IR, XRD, SEM results show that LDH particles were dispersed uniformly in the LLDPE composite films. Particularly, LLDPE composite film with 1% LDH exhibited the optimal performance among all the composite films with a 60.36% enhancement in the water vapor barrier property and a 45.73 °C increase in themore » temperature of maximum mass loss rate compared with pure LLDPE film. Furthermore, the improved infrared absorbance (1180–914 cm{sup −1}) of LLDPE/LDH films revealed the significant enhancement of heat retention. Therefore, this study prompts the application of LLDPE/LDH films as agricultural films with superior heat retention. - Graphical abstract: The fabrication process of LLDPE/LDH composite films. - Highlights: • LDH with basal spacing of 4.07 nm was synthesized by high-energy ball milling. • LLDPE composite films with homogeneous LDH dispersion were fabricated. • The properties of LLDPE/LDH composite films were improved. • LLDPE/LDH composite films show superior heat retention property.« less

Hierarchical layered double hydroxides with Ag nanoparticle modification for ethanol sensing.

PubMed

Qin, Yuxiang; Wang, Liping; Wang, Xiaofei

2018-07-06

Layered double hydroxides (LDHs) have recently been revealed to be promising in gas sensor applications due to their compositional flexibility and unique 2D-interlayer channel for gas diffusion and adsorption. This work demonstrates highly porous hierarchical LDHs containing Mg 2+ and Al 3+ (MgAl-LDHs) for ethanol sensing at room temperature. These MgAl-LDHs, with unique flower-like hierarchical structure and mesoporous interlayer, were synthesized hydrothermally using sodium dodecyl sulfate as soft template as well as intercalating agent. Further modification by discrete Ag nanoparticles (NPs) was achieved via an environmentally friendly glucose-reduction method to improve the gas-sensing response of the LDH-based sensor. It is found that the hierarchical MgAl-LDHs show potential in sensing ethanol gas with rapid dynamic characteristics at room temperature; their response magnitude towards ethanol can be enhanced significantly by Ag NP modification. The gas-response value of the Ag-modified MgAl-LDH sensor is about twice that of pristine MgAl-LDH sensors, towards 5-200 ppm ethanol at room temperature. Meanwhile, rapid response-recovery characteristics are achieved, with response and recovery times shorter than 10 and 50 s, respectively. The satisfactory sensing performance and remarkable response enhancement by Ag NP modification are demonstrated in terms of the unique microstructure of the hierarchical MgAl-LDHs and a constructed conductive effect model of Ag functionalized LDHs.

Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.

PubMed

Liu, Zhaoping; Ma, Renzhi; Osada, Minoru; Iyi, Nobuo; Ebina, Yasuo; Takada, Kazunori; Sasaki, Takayoshi

2006-04-12

This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.

[MoS4]2- Cluster Bridges in Co-Fe Layered Double Hydroxides for Mercury Uptake from S-Hg Mixed Flue Gas.

PubMed

Xu, Haomiao; Yuan, Yong; Liao, Yong; Xie, Jiangkun; Qu, Zan; Shangguan, Wenfeng; Yan, Naiqiang

2017-09-05

[MoS 4 ] 2- clusters were bridged between CoFe layered double hydroxide (LDH) layers using the ion-exchange method. [MoS 4 ] 2- /CoFe-LDH showed excellent Hg 0 removal performance under low and high concentrations of SO 2 , highlighting the potential for such material in S-Hg mixed flue gas purification. The maximum mercury capacity was as high as 16.39 mg/g. The structure and physical-chemical properties of [MoS 4 ] 2- /CoFe-LDH composites were characterized with FT-IR, XRD, TEM&SEM, XPS, and H 2 -TPR. [MoS 4 ] 2- clusters intercalated into the CoFe-LDH layered sheets; then, we enlarged the layer-to-layer spacing (from 0.622 to 0.880 nm) and enlarged the surface area (from 41.4 m 2 /g to 112.1 m 2 /g) of the composite. During the adsorption process, the interlayer [MoS 4 ] 2- cluster was the primary active site for mercury uptake. The adsorbed mercury existed as HgS on the material surface. The absence of active oxygen results in a composite with high sulfur resistance. Due to its high efficiency and SO 2 resistance, [MoS 4 ] 2- /CoFe-LDH is a promising adsorbent for mercury uptake from S-Hg mixed flue gas.

Influence of sodium dodecyl sulfate concentration on the photocatalytic activity and dielectric properties of intercalated sodium dodecyl sulfate into Zn–Cd–Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Abdullah Ahmed Ali, E-mail: abdullah2803@gmail.com; Talib, Zainal Abidin; Hussein, Mohd Zobir

2015-02-15

Highlights: • Zn–Cd–Al–LDH–DS were synthesized with different SDS concentrations. • Photocatalytic activity of samples was improved by increasing SDS concentration. • Dielectric response of LDH can be described by anomalous low frequency dispersion. • The dc conductivity values were calculated for Zn–Cd–Al–LDH–DS samples. • ESR spectra exhibited the successful intercalation of DS molecule into LDH gallery. - Abstract: Sodium dodecyl sulfate (SDS) has been successfully intercalated into Zn–Cd–Al–LDH precursor with different SDS concentrations (0.2, 0.3, 0.4, 0.5 and 1 mol L{sup −1}) using the coprecipitation method at (Zn{sup 2+} + Cd{sup 2+})/Al{sup 3+} molar ratio of 13 and pH 8.more » The structural, morphological, texture and composition properties of the synthesized (Zn–Cd–Al–LDH–DS) nanostructure were investigated using powder X-ray diffraction (PXRD), scanning electron microscope (SEM), thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR), respectively. The photocatalytic activity of these materials was developed by increasing the concentration of intercalated SDS. The absorbance spectra have been used to detect an anion in the LDH interlayer before and after the intercalation process, which confirmed the presence of the dodecyl sulfate (DS{sup −}) anion into LDH gallery after intercalation. The anomalous low frequency dispersion (ALFD) has been used to describe the dielectric response of Zn–Cd–Al–LDH–DS nanostructure using the second type of universal power law. At low frequency, the polarization effect of electrodes caused the rising in dielectric constant and loss values. An important result of the dielectric measurements is the calculated dc conductivity values, which are new in dielectric spectroscopy of LDH materials. An important result of the electron spin resonance (ESR) spectra exhibited the successful intercalation of DS molecule into LDH gallery. The g-factor value was affected by the SDS concentration which indicated changes to the environment around the DS molecule in LDH interlayer.« less

Synthesis and characterization of [4-(2,4-dichlorophenoxybutyrate)-zinc layered hydroxide] nanohybrid

NASA Astrophysics Data System (ADS)

Hussein, Mohd Zobir; Hashim, Norhayati; Yahaya, Asmah Hj.; Zainal, Zulkarnain

2010-05-01

A new layered organic-inorganic nanohybrid material in which an agrochemical, 4-(2,4-dichlorophenoxy)butyrate (DPBA) is intercalated into inorganic interlayers of zinc layered hydroxide (ZLH) was synthesized by direct reaction of aqueous DPBA solution with zinc oxide. The resulting nanohybrid is composed of the organic moieties, DPBA sandwiched between ZLH inorganic interlayers. The nanohybrid afforded well ordered crystalline layered structure, a basal spacing of 29.6 Å, 23.5% carbon (w/w) and 47.9% (w/w) loading of DPBA. FTIR study shows that the absorption bands of the resulting nanohybrid composed the FTIR characteristics of both the DPBA and ZLH which further confirmed the intercalation episode. The intercalated organic moiety in the form of nanohybrid is thermally more stable than its sodium salt. Scanning electron micrograph shows the ZnO precursor has very fine granular structure and transformed into a flake-like when the nanohybrid is formed. This work shows that the nanohybrid of DPBA-ZLH can be synthesized using simple, direct reaction of ZnO and DPBA under aqueous environment for the formation of a new generation of agrochemical.

Interactions and Supramolecular Organization of Sulfonated Indigo and Thioindigo Dyes in Layered Hydroxide Hosts.

PubMed

Costa, Ana L; Gomes, Ana C; Pereira, Ricardo C; Pillinger, Martyn; Gonçalves, Isabel S; Pineiro, Marta; Seixas de Melo, J Sérgio

2018-01-09

Supramolecularly organized host-guest systems have been synthesized by intercalating water-soluble forms of indigo (indigo carmine, IC) and thioindigo (thioindigo-5,5'-disulfonate, TIS) in zinc-aluminum-layered double hydroxides (LDHs) and zinc-layered hydroxide salts (LHSs) by coprecipitation routes. The colors of the isolated powders were dark blue for hybrids containing only IC, purplish blue or dark lilac for cointercalated samples containing both dyes, and ruby/wine for hybrids containing only TIS. The as-synthesized and thermally treated materials were characterized by Fourier transform infrared, Fourier transform Raman, and nuclear magnetic resonance spectroscopies, powder X-ray diffraction, scanning electron microscopy, and elemental and thermogravimetric analyses. The basal spacings found for IC-LDH, TIS-LDH, IC-LHS, and TIS-LHS materials were 21.9, 21.05, 18.95, and 21.00 Å, respectively, with intermediate spacings being observed for the cointercalated samples that either decreased (LDHs) or increased (LHSs) with increasing TIS content. UV-visible and fluorescence spectroscopies (steady-state and time-resolved) were used to probe the molecular distribution of the immobilized dyes. The presence of aggregates together with the monomer units is suggested for IC-LDH, whereas for TIS-LDH, IC-LHS, and TIS-LHS, the dyes are closer to the isolated situation. Accordingly, while emission from the powder H 2 TIS is strongly quenched, an increment in the emission of about 1 order of magnitude was observed for the TIS-LDH/LHS hybrids. Double-exponential fluorescence decays were obtained and associated with two monomer species interacting differently with cointercalated water molecules. The incorporation of both TIS and IC in the LDH and LHS hosts leads to an almost complete quenching of the fluorescence, pointing to a very efficient energy transfer process from (fluorescent) TIS to (nonfluorescent) IC.

Synthesis of [Zn-Al-CO 3] layered double hydroxides by a coprecipitation method under steady-state conditions

NASA Astrophysics Data System (ADS)

Chang, Z.; Evans, D. G.; Duan, X.; Vial, C.; Ghanbaja, J.; Prevot, V.; de Roy, M.; Forano, C.

2005-09-01

A continuous co-precipitation method under steady-state conditions has been investigated for the preparation of nanometer-size layered double hydroxide (LDH) particles using Zn 2Al(OH) 6(CO 3) 0.5·2H 2O as a prototype. The objective was to shorten the preparation time by working without an aging step, using a short and controlled residence time in order to maintain a constant supersaturation level in the reactor and constant particle properties in the exit stream over time. The effects of varying the operating conditions on the structural and textural properties of the LDHs have been studied, including total cation concentration, solvent, residence time, pH and intercalation anion. The products have been characterized using ICP, XRD, FTIR, BET, SEM and TEM. The LDHs prepared by the continuous coprecipitation method have a poorer crystallinity and lower crystallite sizes than those synthesized by the conventional batch method. The results have shown that increasing either cation concentration or the fraction of monoethylene glycol (MEG) in MEG/H 2O mixtures up to 80% (v/v) affect salt solubility and supersaturation, which gives rise to smaller crystallites, larger surface areas and more amorphous compounds. This increase is however limited by the precipitation of zinc and aluminum hydroxides occurring around a total cation concentration of 3.0×10 -1 M in pure water and 3.0×10 -2 M in H 2O/EtOH mixtures. Crystallite size increases with residence time, suggesting a precipitation process controlled by growth. Finally, the continuous coprecipitation method under steady-state conditions has been shown to be a promising alternative to the traditional coprecipitation technique in either pure water or mixed H 2O/MEG solvents.

A One-Step Delamination Procedure to Form Single Sheet Iron(III)-(oxy)Hydroxides

EPA Science Inventory

The dispersion of a layered iron(III)-(oxy)hydroxide intercalated with dodecanoate (oxGR_C12, Fe₃^IIIO_2.18(OH)_3.13(C₁₂H₂₃O₂)_0.56(SO₄)_0.47; derived from the corr...

Behaviour of the surface hydroxide groups of exfoliated kaolinite in the gas phase and during water adsorption.

PubMed

Táborosi, Attila; Szilágyi, Róbert K

2016-02-14

The chemical and physical properties, and thus the reactivity of phylloaluminosilicates can be tailored by intercalation, delamination, and exfoliation processes. In going from the periodic crystalline to the molecular exfoliated phase, surface defects and modifications gain importance as each face of the phylloaluminosilicate comes in direct contact with the external chemical environment. In this work, we extend our earlier studies on the molecular cluster modelling of exfoliated kaolinite sheets by evaluating the positions and orientations of surface hydroxide groups and bridging oxide anions, as the sites of reactivity. The previous focus on the inner chemical environment of a single kaolinite layer is shifted to the surface exposed octahedral aluminium-hydroxide and tetrahedral silicon-oxide sheets. The combination of semi-empirical, ab initio wave function, and density functional calculations unanimously support the amphoteric nature of the surface hydroxide groups with respect to H-bonding donor/acceptor capabilities. To a lesser extent, we observe the same for the bridging oxide anions. This is in contrast to the crystalline phase, which manifests only donor orientation for maintaining an inter-layer H-bond network. These results suggest that both electrophilic and nucleophilic characteristics of the octahedral and tetrahedral sheets need to be considered during intercalation and concomitant exfoliation of the kaolinite sheets.

Geomaterials: their application to environmental remediation

PubMed Central

Yamada, Hirohisa; Tamura, Kenji; Watanabe, Yujiro; Iyi, Nobuo; Morimoto, Kazuya

2011-01-01

Geomaterials are materials inspired by geological systems originating from the billion years long history of the Earth. This article reviews three important classes of geomaterials. The first one is smectites—layered silicates with a cation-exchange capacity. Smectites are useful for removing pollutants and as intercalation compounds, catalysts and polymer nanocomposites. The second class is layered double hydroxides (LDHs). They have an anion-exchange capacity and are used as catalysts, catalyst precursors, sorbents and scavengers for halogens. The third class of geomaterials is zeolites—microporous materials with a cation-exchange capacity which are used for removing harmful cations. Zeolite composites with LDHs can absorb ammonium and phosphate ions in rivers and lakes, whereas zeolite/apatite composites can immobilize the radioactive iodine. These geomaterials are essential for environmental remediation. PMID:27877455

Inorganic nanolayers: structure, preparation, and biomedical applications.

PubMed

Saifullah, Bullo; Hussein, Mohd Zobir B

2015-01-01

Hydrotalcite-like compounds are two-dimensional inorganic nanolayers also known as clay minerals or anionic clays or layered double hydroxides/layered hydroxy salts, and have emerged as a single type of material with numerous biomedical applications, such as drug delivery, gene delivery, cosmetics, and biosensing. Inorganic nanolayers are promising materials due to their fascinating properties, such as ease of preparation, ability to intercalate different type of anions (inorganic, organic, biomolecules, and even genes), high thermal stability, delivery of intercalated anions in a sustained manner, high biocompatibility, and easy biodegradation. Inorganic nanolayers have been the focus for researchers over the last decade, resulting in widening application horizons, especially in the field of biomedical science. These nanolayers have been widely applied in drug and gene delivery. They have also been applied in biosensing technology, and most recently in bioimaging science. The suitability of inorganic nanolayers for application in drug delivery, gene delivery, biosensing technology, and bioimaging science makes them ideal materials to be applied for theranostic purposes. In this paper, we review the structure, methods of preparation, and latest advances made by inorganic nanolayers in such biomedical applications as drug delivery, gene delivery, biosensing, and bioimaging.

Inorganic nanolayers: structure, preparation, and biomedical applications

PubMed Central

Saifullah, Bullo; Hussein, Mohd Zobir B

2015-01-01

Hydrotalcite-like compounds are two-dimensional inorganic nanolayers also known as clay minerals or anionic clays or layered double hydroxides/layered hydroxy salts, and have emerged as a single type of material with numerous biomedical applications, such as drug delivery, gene delivery, cosmetics, and biosensing. Inorganic nanolayers are promising materials due to their fascinating properties, such as ease of preparation, ability to intercalate different type of anions (inorganic, organic, biomolecules, and even genes), high thermal stability, delivery of intercalated anions in a sustained manner, high biocompatibility, and easy biodegradation. Inorganic nanolayers have been the focus for researchers over the last decade, resulting in widening application horizons, especially in the field of biomedical science. These nanolayers have been widely applied in drug and gene delivery. They have also been applied in biosensing technology, and most recently in bioimaging science. The suitability of inorganic nanolayers for application in drug delivery, gene delivery, biosensing technology, and bioimaging science makes them ideal materials to be applied for theranostic purposes. In this paper, we review the structure, methods of preparation, and latest advances made by inorganic nanolayers in such biomedical applications as drug delivery, gene delivery, biosensing, and bioimaging. PMID:26366081

Hydrophobic Modification of Layered Clays and Compatibility for Epoxy Nanocomposites

PubMed Central

Lin, Jiang-Jen; Chan, Ying-Nan; Lan, Yi-Fen

2010-01-01

Recent studies on the intercalation and exfoliation of layered clays with polymeric intercalating agents involving poly(oxypropylene)-amines and the particular uses for epoxy nanocomposites are reviewed. For intercalation, counter-ionic exchange reactions of clays including cationic layered silicates and anionic Al-Mg layered double hydroxide (LDH) with polymeric organic ions afforded organoclays led to spatial interlayer expansion from 12 to 92 Å (X-ray diffraction) as well as hydrophobic property. The inorganic clays of layered structure could be modified by the poly(oxypropylene)amine-salts as the intercalating agents with molecular weights ranging from 230 to 5,000 g/mol. Furthermore, natural montmorillonite (MMT) clay could be exfoliated into thin layer silicate platelets (ca. 1 nm thickness) in one step by using polymeric types of exfoliating agents. Different lateral dimensions of MMT, synthetic fluorinated Mica and LDH clays had been cured into epoxy nanocomposites. The hydrophobic amine-salt modification resulting in high spacing of layered or exfoliation of individual clay platelets is the most important factor for gaining significant improvements of properties. In particular, these modified clays were reported to gain significant improvements such as reduced coefficient of thermal expansion (CTE), enhanced thermal stability, and hardness. The utilization of these layered clays for initiating the epoxy self-polymerization was also reported to have a unique compatibility between clay and organic resin matrix. However, the matrix domain lacks of covalently bonded crosslink and leads to the isolation of powder material. It is generally concluded that the hydrophobic expansion of the clay inter-gallery spacing is the crucial step for enhancing the compatibility and the ultimate preparation of the advanced epoxy materials.

Development of Drug Delivery Systems Based on Layered Hydroxides for Nanomedicine

PubMed Central

Barahuie, Farahnaz; Hussein, Mohd Zobir; Fakurazi, Sharida; Zainal, Zulkarnain

2014-01-01

Layered hydroxides (LHs) have recently fascinated researchers due to their wide application in various fields. These inorganic nanoparticles, with excellent features as nanocarriers in drug delivery systems, have the potential to play an important role in healthcare. Owing to their outstanding ion-exchange capacity, many organic pharmaceutical drugs have been intercalated into the interlayer galleries of LHs and, consequently, novel nanodrugs or smart drugs may revolutionize in the treatment of diseases. Layered hydroxides, as green nanoreservoirs with sustained drug release and cell targeting properties hold great promise of improving health and prolonging life. PMID:24802876

Synthesis and adsorption properties of flower-like layered double hydroxide by a facile one-pot reaction with an eggshell membrane as assistant

NASA Astrophysics Data System (ADS)

Li, Songnan; Zhang, Jiawei; Jamil, Saba; Cai, Qinghai; Zang, Shuying

In this paper, flower-like layered double hydroxides were synthesized with eggshell membrane assistant. The as-prepared samples were characterized by a series of techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Thermal gravity-differential thermal analysis and Nitrogen sorption/desorption. The resulting layered double hydroxides were composed of nanoplates with edge-to-face particle interactions. The specific surface area and total pore volume of the as-prepared flower-like layered double hydroxides were 160m2/g and 0.65m3/g, respectively. The adsorption capacity of flower-like layered double hydroxides to Congo Red was 258mg/g, which was higher than that of layered double hydroxides synthesized by the traditional method.

Fabrication of a novel NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite and its adsorption behavior for Cr(VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Deng, Lin; Shi, Zhou; Wang, Li; Zhou, Shiqing

2017-05-01

A novel magnetic NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite (NiFe2O4/ZnAl-EDTA LDH) was prepared through modified coprecipitation method and employed for adsorptive removal of Cr(VI) from aqueous solution. The adsorbents were characterized using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS). Factors affecting the Cr(VI) adsorption, such as initial solution pH, adsorbent dosage, contact time, initial Cr(VI) concentration, temperature and coexisting ions, were studied systematically. Experiments results show that the magnetic NiFe2O4/ZnAl-EDTA LDH exhibits high adsorption efficiency within a wide pH range of 3.0-7.0 (R>80% at Cr(VI) concentration 50 mg L-1, contact time 360 min, and adsorbent dosage 2 g/L) and quick separation property. The adsorption process is fitted well with the Langmuir isotherm and pseudo-second-order kinetic model. The maximum theoretical adsorption capacity is found to be 77.22 mg g-1 at pH 6.0 and 318 K. The positive ΔH value (2.907 kJ mol-1) and negative ΔG value (-4.722 kJ mol-1) at 298-318 K reveals that the adsorption process is feasible, spontaneous and endothermic. Coexisting anions (PO43-, SO42-, CO32-, HCO3-, Cl-, and NO3-) have no significant effect on Cr(VI) removal. The mechanism study indicates that the adsorption of Cr(VI) onto NiFe2O4/ZnAl-EDTA LDH mainly involves electrostatic attraction and ion exchange interaction. It is interesting to note that a proportion of Cr(VI) adsorbed on the adsorbent surface are reduced to Cr(III) during the adsorption process. Results from this study demonstrate the potential utility of the magnetic NiFe2O4/ZnAl-EDTA LDH that could be developed into a viable technology for efficient removal of Cr(VI) from aqueous solution.

Synthesis and controlled release properties of 2,4-dichlorophenoxy acetate-zinc layered hydroxide nanohybrid

NASA Astrophysics Data System (ADS)

Bashi, Abbas M.; Hussein, Mohd Zobir; Zainal, Zulkarnain; Tichit, Didier

2013-07-01

Direct reaction of ZnO with 2,4-dichlorophenoxyacetic acid (24D) solutions of different concentrations allows obtaining new organic-inorganic nanohybrid materials formed by intercalation of 24D into interlayers of zinc layered hydroxide (ZLH). XRD patterns show a progressive evolution of the structure as 24D concentration increases. The nanohybrid obtained at higher 24D concentration (24D-ZLH(0.4)) reveals a well ordered layered structure with two different basal spacings at 25.2 Å and 24 Å. The FTIR spectrum showing the vibrations bands of the functional groups of 24D and of the ZLH confirms the intercalation. SEM images are in agreement with the structural evolution observed by XRD and reveal the ribbon morphology of the nanohybrids. The release studies of 24D showed a rapid release of 94% for the first 100 min governed by the pseudo-second order kinetic model.

Layered gadolinium hydroxides for simultaneous drug delivery and imaging.

PubMed

Xu, Yadong; Goyanes, Alvaro; Wang, Yuwei; Weston, Andrew J; So, Po-Wah; Geraldes, Carlos F G C; Fogg, Andrew M; Basit, Abdul W; Williams, Gareth R

2018-02-27

The potential of the layered gadolinium hydroxide (LGdH) [Gd 2 (OH) 5 ]Cl·yH 2 O (LGdH-Cl) for simultaneous drug delivery and magnetic resonance imaging was explored in this work. Three non-steroidal anti-inflammatory drugs (diclofenac [dic], ibuprofen [ibu], and naproxen [nap]) were intercalated into LGdH-Cl for the first time, using three different routes (ion exchange intercalation, coprecipitation, and exfoliation-self-assembly). X-ray diffraction, elemental microanalysis and IR spectroscopy confirmed successful incorporation of the drug into the interlayer spaces of the LGdH in all cases. From a comparison of the guest anion sizes and interlayer spacings, the active ingredients are believed to adopt intertwined bilayer configurations between the LGdH layers. The materials prepared by coprecipitation in general have noticeably higher drug loadings than those produced by ion exchange or self-assembly, as a result of the incorporation of some neutral drug into the composites. The LGdH-drug intercalates are stable at neutral pH, but rapidly degrade in acidic conditions to free Gd 3+ into solution. While LGdH-nap releases its drug loading into solution very rapidly (within ca. 1.5 h) at pH 7.4, LGdH-dic shows sustained release over 4 h, and LGdH-ibu extends this to 24 h. The latter composites therefore can be incorporated into enteric-coated tablets to provide sustained release in the small intestine. The drug intercalates are highly biocompatible and retain the proton relaxivity properties of the parent LGdH-Cl, with the materials most promising for use as negative contrast agents in MRI. Overall, the LGdH-drug intercalation compounds appear to have great potential for use in theranostic applications.

Aging-Resistant Functionalized LDH⁻SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism.

PubMed

Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui; Wang, Xin

2018-05-18

With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH⁻SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH⁻SAS composites. Successful preparation of LDH⁻SAS was confirmed by XRD, TGA and FTIR. LDH⁻SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH⁻SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance.

Aging-Resistant Functionalized LDH–SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism

PubMed Central

Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui

2018-01-01

With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH–SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH–SAS composites. Successful preparation of LDH–SAS was confirmed by XRD, TGA and FTIR. LDH–SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH–SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance. PMID:29783656

The intercalation chemistry of layered iron chalcogenide superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vivanco, Hector K.; Rodriguez, Efrain E., E-mail: efrain@umd.edu

The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the rolemore » of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.« less

A facile synthesis of strong near infrared fluorescent layered double hydroxide nanovehicles with an anticancer drug for tumor optical imaging and therapy

NASA Astrophysics Data System (ADS)

Chen, Chunping; Yee, Lee Kim; Gong, Hua; Zhang, Yong; Xu, Rong

2013-05-01

In this work, a new multifunctional nanovehicle for tumor optical imaging and therapy was developed using Y2O3:Er3+,Yb3+ nanoparticles as near infrared fluorescent nanophosphors, and MgAl-layered double hydroxide (LDH) nanosheets as anticancer drug nanovehicles. Monodispersed Y2O3:Er3+,Yb3+ nanophosphors were readily synthesized by the urea assisted homogenous precipitation method. Hierarchically structured LDH nanosheets intercalated with an anticancer drug, fluorouracil (5FU), were deposited on the surface of Y2O3:Er3+,Yb3+@SiO2 by a simple precipitation method followed by hydrothermal treatment. The resultant Y2O3:Er3+,Yb3+@SiO2@LDH-5FU nanovehicles exhibit strong red upconversion fluorescence under the excitation of a 980 nm laser, which allows tracking of the nanovehicles after localization in cancer cells. A better anticancer efficiency was obtained over the nanovehicles than the free drug which can be attributed to their positively charged surfaces for favorable interaction with the negatively charged cell membranes. The multifunctional nanovehicles designed in this work are expected to be promising material candidates for simultaneous tumor optical imaging and therapy.In this work, a new multifunctional nanovehicle for tumor optical imaging and therapy was developed using Y2O3:Er3+,Yb3+ nanoparticles as near infrared fluorescent nanophosphors, and MgAl-layered double hydroxide (LDH) nanosheets as anticancer drug nanovehicles. Monodispersed Y2O3:Er3+,Yb3+ nanophosphors were readily synthesized by the urea assisted homogenous precipitation method. Hierarchically structured LDH nanosheets intercalated with an anticancer drug, fluorouracil (5FU), were deposited on the surface of Y2O3:Er3+,Yb3+@SiO2 by a simple precipitation method followed by hydrothermal treatment. The resultant Y2O3:Er3+,Yb3+@SiO2@LDH-5FU nanovehicles exhibit strong red upconversion fluorescence under the excitation of a 980 nm laser, which allows tracking of the nanovehicles after localization in cancer cells. A better anticancer efficiency was obtained over the nanovehicles than the free drug which can be attributed to their positively charged surfaces for favorable interaction with the negatively charged cell membranes. The multifunctional nanovehicles designed in this work are expected to be promising material candidates for simultaneous tumor optical imaging and therapy. Electronic supplementary information (ESI) available: TEM images of Y2O3:Er3+,Yb3+@SiO2 synthesized by using different amounts of TEOS, and confocal scanning laser microscopy images (Z stack) of MCF-7 cells incubated with Y2O3:Er3+,Yb3+@SiO2@LDH-5FU for 30 min and 24 h. See DOI: 10.1039/c3nr00781b

Organo-modified anionic clays into polymer compared to smectite-type nanofiller: potential applications of the nanocomposites.

PubMed

Leroux, Fabrice

2006-02-01

The scope of the article is to provide the state of the art concerning the utilization of Layered Double Hydroxide (LDH) materials in polymer nanocomposite and to enlight their potential application and even advantage in comparison to smectite-type materials. A particular attention is paid on the synthetic procedures for the elaboration of polymer nanocomposite taking poly(styrene), poly(imide), poly(methylmethacrylate) and epoxy resin as examples. Lipophilization of the inorganic platelets used to decrease the surface polarity may be achieved either with a surfactant molecule or a surfactant monomer molecule, giving rise to reactive hybrid filler. The state of dispersion of the inorganic platelets, i.e., intercalated versus exfoliated structure is discussed. LDH-based nanocomposites present mechanical properties, such as the tensile modulus and elongation at break, always greater in comparison to virgin polymer, but also compete well with smectite-type filler. For epoxy nanocomposite, the relative gain using LDH nanofiller is superior to smectite-type filler. In both types of nanocomposites using either LDH or smectite-type nanofiller, mixed intercalated-exfoliated structure is generally met. Dispersion of LDH nanoplatelets should emerge well as flame-retardant materials and as polymer electrolyte, but may also find application in topical domains such as in sun radiation absorption.

Anticancer nanodelivery system with controlled release property based on protocatechuate–zinc layered hydroxide nanohybrid

PubMed Central

Barahuie, Farahnaz; Hussein, Mohd Zobir; Abd Gani, Shafinaz; Fakurazi, Sharida; Zainal, Zulkarnain

2014-01-01

Background We characterize a novel nanocomposite that acts as an efficient anticancer agent. Methods This nanocomposite consists of zinc layered hydroxide intercalated with protocatechuate (an anionic form of protocatechuic acid), that has been synthesized using a direct method with zinc oxide and protocatechuic acid as precursors. Results The resulting protocatechuic acid nanocomposite (PAN) showed a basal spacing of 12.7 Å, indicating that protocatechuate was intercalated in a monolayer arrangement, with an angle of 54° from the Z-axis between the interlayers of the zinc layered hydroxide, and an estimated drug loading of about 35.7%. PAN exhibited the properties of a mesoporous type material, with greatly enhanced thermal stability of protocatechuate as compared to its free counterpart. The presence of protocatechuate in the interlayers of the zinc layered hydroxide was further supported by Fourier transform infrared spectroscopy. Protocatechuate was released from PAN in a slow and sustained manner. This mechanism of release was well represented by a pseudo-second order kinetics model. PAN has shown increased cytotoxicity compared to the free form of protocatechuic acid in all cancer cell lines tested. Tumor growth suppression was extensive, particularly in HepG2 and HT29 cell lines. Conclusion PAN is suitable for use as a controlled release formulation, and our in vitro evidence indicates that PAN is an effective anticancer agent. PAN may have potential as a chemotherapeutic drug for human cancer. PMID:25061291

Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

NASA Astrophysics Data System (ADS)

Jin, Miao; Li, Wanjing; Spillane, Dominic E. M.; Geraldes, Carlos F. G. C.; Williams, Gareth R.; Bligh, S. W. Annie

2016-03-01

A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn5(OH)8]Cl2·yH2O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10-12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.

Direct growth of 2D nickel hydroxide nanosheets intercalated with polyoxovanadate anions as a binder-free supercapacitor electrode.

PubMed

Gunjakar, Jayavant L; Inamdar, Akbar I; Hou, Bo; Cha, SeungNam; Pawar, S M; Abu Talha, A A; Chavan, Harish S; Kim, Jongmin; Cho, Sangeun; Lee, Seongwoo; Jo, Yongcheol; Kim, Hyungsang; Im, Hyunsik

2018-05-17

A mesoporous nanoplate network of two-dimensional (2D) layered nickel hydroxide Ni(OH)2 intercalated with polyoxovanadate anions (Ni(OH)2-POV) was built using a chemical solution deposition method. This approach will provide high flexibility for controlling the chemical composition and the pore structure of the resulting Ni(OH)2-POV nanohybrids. The layer-by-layer ordered growth of the Ni(OH)2-POV is demonstrated by powder X-ray diffraction and cross-sectional high-resolution transmission electron microscopy. The random growth of the intercalated Ni(OH)2-POV nanohybrids leads to the formation of an interconnected network morphology with a highly porous stacking structure whose porosity is controlled by changing the ratio of Ni(OH)2 and POV. The lateral size and thickness of the Ni(OH)2-POV nanoplates are ∼400 nm and from ∼5 nm to 7 nm, respectively. The obtained thin films are highly active electrochemical capacitor electrodes with a maximum specific capacity of 1440 F g-1 at a current density of 1 A g-1, and they withstand up to 2000 cycles with a capacity retention of 85%. The superior electrochemical performance of the Ni(OH)2-POV nanohybrids is attributed to the expanded mesoporous surface area and the intercalation of the POV anions. The experimental findings highlight the outstanding electrochemical functionality of the 2D Ni(OH)2-POV nanoplate network that will provide a facile route for the synthesis of low-dimensional hybrid nanomaterials for a highly active supercapacitor electrode.

Preparation, characterization and dye adsorption of Au nanoparticles/ZnAl layered double oxides nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Yu Xin; Hao, Xiao Dong; Kuang, Min; Zhao, Han; Wen, Zhong Quan

2013-10-01

In this work, Au/ZnAl-layer double oxides (LDO) nanocomposties were prepared through a facile calcination process of AuCl4- intercalated ZnAl-layered double hydroxides (LDHs) nanocomposites. The morphology and crystal structure of these nanocomposites were characterized by Scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and N2 sorption analysis. By tailoring the process parameter, such as calcination temperature, heating time and the component composition, the adsorption properties of methyl orange (MO) on the Au/ZnAl-LDO nanocomposites were investigated in this work. In a typical adsorption process, it was found that 0.985 mg of MO (0.01 g L-1, 100 mL, 1 mg of MO in total) can be removed in 60 min by utilizing only 2.5 mg of Au/ZnAl-LDO (Au content, 1%) as adsorbents. Our adsorption data obtained from the Langmuir model also gave good values of the determination coefficient, and the saturated adsorption capacity of Au/ZnAl-LDO nanocomposites for MO was found to be 627.51 mg/g under ambient condition (e.g., room temperature, 1 atm). In principle, these hybrid nanostructures with higher adsorption abilities could be very promising adsorbents for wastewater treatment.

Enrichment of rare earth metal ions by the highly selective adsorption of phytate intercalated layered double hydroxide.

PubMed

Jin, Cheng; Liu, Huimin; Kong, Xianggui; Yan, Hong; Lei, Xiaodong

2018-02-27

Phytate intercalated MgAl layered double hydroxide (MgAl-LDH) was prepared by an anion exchange method with the precursor NO 3 - containing MgAl-LDH. The final as-synthesized product [Mg 0.69 Al 0.31 (OH) 2 ] (phytateNa 6 ) 0.05 (NO 3 ) 0.01 ·mH 2 O (phytate-LDH) has highly selective adsorption ability for some metal ions and can be used to enrich rare earth metal ions in mixed solution, such as Pr 3+ and Ce 3+ from a mixed solution of them with Pb 2+ and Co 2+ . At first, phytate-LDH has good adsorption performance for these ions in single metal ion solutions. At low concentration (below 10 mg L -1 ), all the capture rates of the four metal ions were more than 97%, for highly toxic Pb 2+ it was even up to nearly 100%, and a high capture rate (99.87%) was maintained for Pb 2+ at a high concentration (100 mg L -1 ). When all the four metal ions are co-existing in aqueous solution, the selectivity order is Pb 2+ ≫ Pr 3+ ≈ Ce 3+ > Co 2+ . In a solution containing mixtures of the three metal ions of Pr 3+ , Ce 3+ , and Co 2+ , the selectivity order is Pr 3+ ≈ Ce 3+ ≫ Co 2+ , and in a solution containing mixtures of Pr 3+ with Co 2+ and Ce 3+ with Co 2+ , the selectivity orders are Pr 3+ ≫ Co 2+ and Ce 3+ ≫ Co 2+ , respectively. The high selectivity and adsorption capacities for Pb 2+ , Co 2+ , Pr 3+ , and Ce 3+ result in the efficient removal of Pb 2+ and enrichment of the rare earth metal ions Pr 3+ and Ce 3+ by phytate-LDH. Based on the elemental analysis, it is found that the difference of the adsorption capacities is mainly due to the different coordination number of them with phytate-LDH. With molecular simulation, we believe that the adsorption selectivity is due to the difference of the binding energy between the metal ion and phytate-LDH. Therefore, the phytate-LDH is promising for the enrichment and/or purification of the rare earth metal ions and removal of toxic metal ions from waste water.

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.

1999-01-01

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Nickel hydroxides and related materials: a review of their structures, synthesis and properties

PubMed Central

Hall, David S.; Lockwood, David J.; Bock, Christina; MacDougall, Barry R.

2015-01-01

This review article summarizes the last few decades of research on nickel hydroxide, an important material in physics and chemistry, that has many applications in engineering including, significantly, batteries. First, the structures of the two known polymorphs, denoted as α-Ni(OH)2 and β-Ni(OH)2, are described. The various types of disorder, which are frequently present in nickel hydroxide materials, are discussed including hydration, stacking fault disorder, mechanical stresses and the incorporation of ionic impurities. Several related materials are discussed, including intercalated α-derivatives and basic nickel salts. Next, a number of methods to prepare, or synthesize, nickel hydroxides are summarized, including chemical precipitation, electrochemical precipitation, sol–gel synthesis, chemical ageing, hydrothermal and solvothermal synthesis, electrochemical oxidation, microwave-assisted synthesis, and sonochemical methods. Finally, the known physical properties of the nickel hydroxides are reviewed, including their magnetic, vibrational, optical, electrical and mechanical properties. The last section in this paper is intended to serve as a summary of both the potentially useful properties of these materials and the methods for the identification and characterization of ‘unknown’ nickel hydroxide-based samples. PMID:25663812

Ab initio simulation of changes in geometry, electronic structure, and Gibbs free energy caused by dehydration of hydrotalcites containing Cl⁻ and CO₃²⁻ counteranions.

PubMed

Costa, Deyse G; Rocha, Alexandre B; Souza, Wladmir F; Chiaro, Sandra Shirley X; Leitão, Alexandre A

2011-04-07

This ab initio study was performed to better understand the correlation between intercalated water molecules and layered double hydroxides (LDH), as well as the changes that occur by the dehydration process of Zn-Al hydrotalcite-like compounds containing Cl⁻ and CO₃²⁻ counterions. We have verified that the strong interaction among intercalated water molecules, cointercalated anions, and OH groups from hydroxyl layers is reflected in the thermal stability of these compounds. The Zn(2/3)Al(1/3)(OH)₂Cl(1/3)·2/3H₂O hydrotalcite loses all the intercalated water molecules around 125 °C, while the Zn(2/3)Al(1/3)(OH)₂(CO₃)(1/6)·4/6H₂O compound dehydrates at about 175 °C. These values are in good agreement with experimental data. The interlayer interactions were discussed on the basis of electron density difference analyses. Our calculation shows that the electron density in the interlayer region decreases during the dehydration process, inducing the migration of the Cl⁻ anion and the displacement of the hydroxyl layer from adjacent layers. Changes in these compound structures occur to recover part of the hydrogen bonds broken due to the removal of water molecules. It was observed that the chloride ion had initially a lower Löwdin charge (Cl(-0.43)), which has increased its absolute value (Cl(-0.58)) after the water molecules removal, while the charges on carbonate ions remain invariant, leading to the conclusion that the Cl⁻ anion can be more influenced by the amount of water molecules in the interlayer space than the CO₃²⁻ anion in hydrotalcite-like compounds.

Kaolinite Nanocomposite Platelets Synthesized by Intercalation and Imidization of Poly(styrene-co-maleic anhydride)

PubMed Central

Samyn, Pieter; Schoukens, Gustaaf; Stanssens, Dirk

2015-01-01

A synthesis route is presented for the subsequent intercalation, exfoliation and surface modification of kaolinite (Kln) by an imidization reaction of high-molecular weight poly(styrene-co-maleic anhydride) or SMA in the presence of ammonium hydroxide. In a first step, the intercalation of ammonolyzed SMA by guest displacement of intercalated dimethylsulfoxide has been proven. In a second step, the imidization of ammonolyzed SMA at 160 °C results in exfoliation of the kaolinite layers and deposition of poly(styrene-co-maleimide) or SMI nanoparticles onto the kaolinite surfaces. Compared with a physical mixture of Kln/SMI, the chemically reacted Kln/SMI provides more efficient exfoliation and hydrogen bonding between the nanoparticles and the kaolinite. The kaolinite nanocomposite particles are synthesized in aqueous dispersion with solid content of 65 wt %. The intercalation and exfoliation are optimized for a concentration ratio of Kln/SMI = 70:30, resulting in maximum intercalation and interlayer distance in combination with highest imide content. After thermal curing at 135 °C, the imidization proceeds towards a maximum conversion of the intermediate amic acid moieties. The changes in O–H stretching and kaolinite lattice vibrations have been illustrated by infrared and FT-Raman spectroscopy, which allow for a good quantification of concentration and imidization effects. PMID:28793445

Synthesis and controlled release properties of 2,4-dichlorophenoxy acetate–zinc layered hydroxide nanohybrid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bashi, Abbas M., E-mail: abbasmatrood@yahoo.com; Hussein, Mohd Zobir; Zainal, Zulkarnain

2013-07-15

Direct reaction of ZnO with 2,4-dichlorophenoxyacetic acid (24D) solutions of different concentrations allows obtaining new organic–inorganic nanohybrid materials formed by intercalation of 24D into interlayers of zinc layered hydroxide (ZLH). XRD patterns show a progressive evolution of the structure as 24D concentration increases. The nanohybrid obtained at higher 24D concentration (24D–ZLH(0.4)) reveals a well ordered layered structure with two different basal spacings at 25.2 Å and 24 Å. The FTIR spectrum showing the vibrations bands of the functional groups of 24D and of the ZLH confirms the intercalation. SEM images are in agreement with the structural evolution observed by XRDmore » and reveal the ribbon morphology of the nanohybrids. The release studies of 24D showed a rapid release of 94% for the first 100 min governed by the pseudo-second order kinetic model. - Graphical abstract: The phenomenon indicates that the optical energy gap is enlarged with the increase of molar concentrations in 2,4-dichlorophenoxy acetate anion content into ZnO to create a ZLH–24D nanohybrid. - Highlights: • Nanohybrid was synthesized from 2,4-dichlorophenoxy acetate with-Zinc LHD, using wet chemistry. • Characterized using SEM, TEM, EDX, FTIR, XRD and TGA. • Ribbon-shaped 24D–Zn-layered hydroxide nanoparticles with (003) diffractions of 2.5 nm phase were synthesized.« less

Synthesis, characterization and application of two-dimensional layered metal hydroxides for environmental remediation purposes

NASA Astrophysics Data System (ADS)

Machingauta, Cleopas

Two-dimensional layered nano composites, which include layered double hydroxides (LDHs), hydroxy double salts (HDSs) and layered hydroxide salts (LHSs) are able to intercalate different molecular species within their gallery space. These materials have a tunable structural composition which has made them applicable as fire retardants, adsorbents, catalysts, catalyst support materials, and ion exchangers. Thermal treatment of these materials results in destruction of the layers and formation of mixed metal oxides (MMOs) and spinels. MMOs have the ability to adsorb anions from solution and may also regenerate layered structures through a phenomenon known as memory effect. Zinc-nickel hydroxy nitrate was used for the uptake of a series of halogenated acetates (HAs). HAs are pollutants introduced into water systems as by-products of water chlorination and pesticide degradation; their sequestration from water is thus crucial. Optimization of layered materials for controlled uptake requires an understanding of their ion-exchange kinetics and thermodynamics. Exchange kinetics of these anions was monitored using ex-situ PXRD, UV-vis, HPLC and FTIR. It was revealed that exchange rates and uptake efficiencies are related to electronic spatial extents and the charge on carboxyl-oxygen atoms. In addition, acetate and nitrate-based HDSs were used to explore how altering the hydroxide layer affects uptake of acetate/nitrate ions. Changing the metal identities affects the interaction of the anions with the layers. From FTIR, we observed that nitrates coordinate in a D3h and Cs/C 2v symmetry; the nitrates in D3h symmetry were easily exchangeable. Interlayer hydrogen bonding was also revealed to be dependent on metal identity. Substituting divalent cations with trivalent cations produces materials with a higher charge density than HDSs and LHSs. A comparison of the uptake efficiency of zinc-aluminum, zinc-gallium and zinc-nickel hydroxy nitrates was performed using trichloroacetic acid as target anion. Uptake efficiency was better for LDHs than HDS, and between the LDHs, zinc-aluminum hydroxy nitrate was the best material for the uptake of tClAc. Calcined LDHs were applied for the uptake of methyl-orange, model azo-dye. The ability to regenerate the layered structures was helpful for improving adsorption efficiency. It has been reveal that calcined LDHs are also better adsorbents than calcined HDSs.

Preparation and structural characterization of zwitterionic surfactant intercalated into NiZn-layered hydroxide salts

NASA Astrophysics Data System (ADS)

Liu, Jiexiang; Wang, Jianlong; Zhang, Xiaoguang; Fang, Binbin; Hu, Pan; Zhao, Xuyang

2015-10-01

Three zwitterionic surfactants, dodecyl dimethyl carboxylbetaine (DCB), dodecyl dimethyl sulfobetaine (DSB) and N-dodecyl-β-aminoprpionate (DAP), intercalated into NiZn-layered hydroxide salts (NZL-DCB, NZL-DSB and NZL-DAP) were synthesized by the coprecipitation method. The effect of surfactant content, pH, temperature and time of hydrothermal treatment on preparation was investigated and discussed. The NZL-DCB, NZL-DSB and NZL-DAP were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry analysis and differential thermal analysis (TGA/DTA). The results showed that basal spacings of NZL-DCB, NZL-DSB and NZL-DAP were around 3.45, 3.68 and 3.94 nm, respectively. DCB, DSB and DAP probably form an overlapped bilayer in the gallery. TGA/DTA data indicated that NZL-DCB, NZL-DSB and NZL-DAP displayed three loss weight stages: loss of adsorbed and structural water, dehydroxylation of matrix and decomposition of nitrate ions, decomposition and combustion of surfactants. Furthermore, chemical analysis data, BET surface area and scanning electron microscopic (SEM) were also measured and analyzed.

Layered double hydroxide catalyst for the conversion of crude vegetable oils to a sustainable biofuel

NASA Astrophysics Data System (ADS)

Mollaeian, Keyvan

Over the last two decades, the U.S. has developed the production of biodiesel, a mixture of fatty acid methyl esters, using chiefly vegetable oils as feedstocks. However, there is much concern about the availability of high-quality vegetable oils for longterm biodiesel production. Problems have also risen due to the production of glycerol, an unwanted byproduct, as well as the need for process wash water. Therefore, this study was initiated to produce not only fatty acid methyl esters (FAMEs) but also fatty acid glycerol carbonates (FAGCs) by replacing methanol with dimethyl carbonate (DMC). The process would have no unnecessary byproducts and would be a simplified process compared to traditional biodiesel. In addition, this altering of the methylating agent could convert triglycerides, free fatty acids, and phospholipids to a sustainable biofuel. In this project, Mg-Al Layered Double Hydroxide (LDH) was optimized by calcination in different temperature varied from 250°C to 450°C. The gallery between layers was increased by intercalating sodium dodecylsulfate (SDS). During catalyst preparation, the pH was controlled ~10. In our experiment, triazabicyclodecene (TBD) was attached with trimethoxysilane (3GPS) as a coupling agent, and N-cetyl-N,N,N-trimethylammonium bromide (CTAB) was added to remove SDS from the catalyst. The catalyst was characterized by XRD, FTIR, and Raman spectroscopy. The effect of the heterogeneous catalyst on the conversion of canola oil, corn oil, and free fatty acids was investigated. To analyze the conversion of lipid oils to biofuel an in situ Raman spectroscopic method was developed. Catalyst synthesis methods and a proposed mechanism for converting triglycerides and free fatty acids to biofuel will be presented.

Stimuli-responsive hybrid materials: breathing in magnetic layered double hydroxides induced by a thermoresponsive molecule

DOE PAGES

Abellán, Gonzalo; Jordá, Jose Luis; Atienzar, Pedro; ...

2014-12-04

In this study, a hybrid magnetic multilayer material of micrometric size, with highly crystalline hexagonal crystals consisting of CoAl–LDH ferromagnetic layers intercalated with thermoresponsive 4-(4 anilinophenylazo)benzenesulfonate (AO5) molecules diluted (ratio 9 : 1) with a flexible sodium dodecylsulphate (SDS) surfactant has been obtained. The resulting material exhibits thermochromism attributable to the isomerization between the azo (prevalent at room temperature) and the hydrazone (favoured at higher temperatures) tautomers, leading to a thermomechanical response. In fact, these crystals exhibited thermally induced motion triggering remarkable changes in the crystal morphology and volume. In situ variable temperature XRD of these thin hybrids shows thatmore » the reversible change into the two tautomers is reflected in a shift of the position of the diffraction peaks at high temperatures towards lower interlayer spacing for the hydrazone form, as well as a broadening of the peaks reflecting lower crystallinity and ordering due to non-uniform spacing between the layers. These structural variations between room temperature (basal spacing (BS) = 25.91 Å) and 100 °C (BS = 25.05 Å) are also reflected in the magnetic properties of the layered double hydroxide (LDH) due to the variation of the magnetic coupling between the layers. Finally and in conclusion, our study constitutes one of the few examples showing fully reversible thermo-responsive breathing in a 2D hybrid material. In addition, the magnetic response of the hybrid can be modulated due to the thermotropism of the organic component that, by influencing the distance and in-plane correlation of the inorganic LDH, modulates the magnetism of the CoAl–LDH sheets in a certain range.« less

Hydroxy double salts loaded with bioactive ions: Synthesis, intercalation mechanisms, and functional performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaassis, Abdessamad Y.A.; Xu, Si-Min; Guan, Shanyue

The intercalation of the anions of diclofenac (Dic), naproxen (Nap), and valproic acid (Val) into three hydroxy double salts (HDSs) has been explored in this work. Experiments were performed with [Co{sub 1.2}Zn{sub 3.8}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (CoZn-NO{sub 3}), [Ni{sub 2}Zn{sub 3}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (NiZn-NO{sub 3}) and [Zn{sub 5}(OH){sub 8}](NO{sub 3}){sub 2}·2H{sub 2}O (Zn-NO{sub 3}). It proved possible to intercalate diclofenac and naproxen into all three HDSs. In contrast, Val could be intercalated into CoZn-NO{sub 3} but when it was reacted with Zn-NO{sub 3} the HDS structure was destroyed, and the product comprised ZnO. Successful intercalation was verifiedmore » by X-ray diffraction, IR spectroscopy, and elemental microanalysis. Molecular dynamics simulations showed the Dic and Nap ions to arrange themselves in an “X” shape in the interlayer space, forming a bilayer. Val was found to adopt a position with its aliphatic groups parallel to the HDS layer, again in a bilayer. In situ time resolved X-ray diffraction experiments revealed that intercalation of Dic and Nap into CoZn-NO{sub 3} and Zn-NO{sub 3} is mechanistically complex, with a number of intermediate phases observed. In contrast, the intercalation of all three guests into NiZn-NO{sub 3} and of Val into CoZn-NO{sub 3} are simple one step reactions proceeding directly from the starting material to the product. The HDS-drug composites were found to have sustained release profiles. - Graphical abstract: Seven new drug intercalates of hydroxy double salts (HDSs) have been prepared and characterised. The intercalation mechanisms have been explored, and the drug release properties of the HDS/drug composites quantified. Display Omitted.« less

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, Kathleen C.; Winans, Randall E.; Botto, Robert E.

1994-01-01

A method for incorporating diverse Varieties of intercalants or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalant or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalants or templates may be introduced. The intercalants or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays.

Organic or organometallic template mediated clay synthesis

DOEpatents

Gregar, K.C.; Winans, R.E.; Botto, R.E.

1994-05-03

A method is described for incorporating diverse varieties of intercalates or templates directly during hydrothermal synthesis of clays such as hectorite or montmorillonite-type layer-silicate clays. For a hectorite layer-silicate clay, refluxing a gel of silica sol, magnesium hydroxide sol and lithium fluoride for two days in the presence of an organic or organometallic intercalate or template results in crystalline products containing either (a) organic dye molecules such as ethyl violet and methyl green, (b) dye molecules such as alcian blue that are based on a Cu(II)-phthalocyannine complex, or (c) transition metal complexes such as Ru(II)phenanthroline and Co(III)sepulchrate or (d) water-soluble porphyrins and metalloporphyrins. Montmorillonite-type clays are made by the method taught by U.S. Pat. No. 3,887,454 issued to Hickson, Jun. 13, 1975; however, a variety of intercalates or templates may be introduced. The intercalates or templates should have (i) water-solubility, (ii) positive charge, and (iii) thermal stability under moderately basic (pH 9-10) aqueous reflux conditions or hydrothermal pressurized conditions for the montmorillonite-type clays. 22 figures.

Novel inorganic materials for polymer electrolyte and alkaline fuel cells

NASA Astrophysics Data System (ADS)

Tadanaga, Kiyoharu

2012-06-01

Inorganic materials with high ionic conductivity must have big advantages for the thermal and long term stability when the materials are used as the electrolyte of fuel cells. In the present paper, novel ionic conductive inorganic materials for polymer electrolyte fuel cells (PEFCs) and all solid state alkaline fuel cells (AFCs) that have been developed by our group have been reviewed. PEFCs which can operate in temperature range from 100 to 200 °C are intensively studied because of some advantages such as reduction of CO poisoning of Pt catalyst and acceleration of electrode reactions. We showed that the fuel cells using the composite membranes prepared from phosphosilicate gel powder and polyimide precursor can operate in the temperature range from 30 to 180 °C. We also found that the inorganic-organic hybrid membranes with acid-base pairs from 3-aminopropyl triethoxy silane and H2SO4 or H3PO4 show high proton conductivity under dry atmosphere, and the membranes are thermally stable at intermediate temperatures. On the other hand, because the use of noble platinum is the serious problem for the commercialization of PEFCs and because oxidation reactions are usually faster than those of acid-type fuel cells, alkaline type fuel cells, in which a nonplatinum catalyst can be used, are attractive. Recently, we have proposed an alkaline-type direct ethanol fuel cell (DEFC) using a natural clay electrolyte with non-platinum catalysts. So-called hydrotalcite clay, Mg-Al layered double hydroxide intercalated with CO32- (Mg-Al CO32- LDH), has been proved to be a hydroxide ion conductor. An alkalinetype DEFC using Mg-Al CO32- LDH as the electrolyte and aqueous solution of ethanol and potassium hydroxide as a source of fuel exhibited excellent electrochemical performance.

One-dimensional nanowires of pseudoboehmite (aluminum oxyhydroxide γ-AlOOH)

PubMed Central

Iijima, Sumio; Yumura, Takashi; Liu, Zheng

2016-01-01

We report the discovery of a 1D crystalline structure of aluminum oxyhydroxide. It was found in a commercial product of fibrous pseudoboehmite (PB), γ-AlOOH, synthesized easily with low cost. The thinnest fiber found was a ribbon-like structure of only two layers of an Al–O octahedral double sheet having a submicrometer length along its c axis and 0.68-nm thickness along its b axis. This thickness is only slightly larger than half of the lattice parameter of the b-axis unit cell of the boehmite crystal (b/2 = 0.61 nm). Moreover, interlayer splittings having an average width of 1 nm inside the fibrous PB are found. These wider interlayer spaces may have intercalation of water, which is suggested by density functional theory (DFT) calculation. The fibers appear to grow as almost isolated individual filaments in aqueous Al-hydroxide sols and the growth direction of fibrous PB is always along its c axis. PMID:27708158

Controlled-release formulation of antihistamine based on cetirizine zinc-layered hydroxide nanocomposites and its effect on histamine release from basophilic leukemia (RBL-2H3) cells

PubMed Central

Hasan, Samer; Ali, Hussein Al; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Ismail, Maznah; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

2012-01-01

A controlled-release formulation of an antihistamine, cetirizine, was synthesized using zinc-layered hydroxide as the host and cetirizine as the guest. The resulting well-ordered nanolayered structure, a cetirizine nanocomposite “CETN,” had a basal spacing of 33.9 Å, averaged from six harmonics observed from X-ray diffraction. The guest, cetirizine, was arranged in a horizontal bilayer between the zinc-layered hydroxide (ZLH) inorganic interlayers. Fourier transform infrared spectroscopy studies indicated that the intercalation takes place without major change in the structure of the guest and that the thermal stability of the guest in the nanocomposites is markedly enhanced. The loading of the guest in the nanocomposites was estimated to be about 49.4% (w/w). The release study showed that about 96% of the guest could be released in 80 hours by phosphate buffer solution at pH 7.4 compared with about 97% in 73 hours at pH 4.8. It was found that release was governed by pseudo-second order kinetics. Release of histamine from rat basophilic leukemia cells was found to be more sensitive to the intercalated cetirizine in the CETN compared with its free counterpart, with inhibition of 56% and 29%, respectively, at 62.5 ng/mL. The cytotoxicity assay toward Chang liver cells line show the IC50 for CETN and ZLH are 617 and 670 μg/mL, respectively. PMID:22848164

Intercalation of Cobalt into the Interlayer of Birnessite Improves Oxygen Evolution Catalysis

DOE PAGES

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; ...

2016-10-10

Here we show that the activity of cobalt for the oxygen evolution reaction (OER) can be enhanced by confining it in the interlayer region of birnessite (layered manganese oxide). The cobalt intercalation was verified by employing state-of-the-art characterization techniques such as XRD, Raman and electron microscopy. It is demonstrated that the Co 2+/birnessite electrocatalyst can reach 10 mA cm -2 at an overpotential of 360 mV with near unity Faradaic efficiency. This overpotential is lower than that which can be achieved by using a pure cobalt hydroxide electrocatalyst for the OER. Furthermore, the Co 2+/birnessite catalyst shows no degradation aftermore » 1000 electrochemical cycles.« less

Green Rust: Its Electrochemical Generation, Characterization, and Implications

DTIC Science & Technology

2009-02-01

FeOOH), and lepidocrocite ( γ -FeOOH) in well-aerated systems, and hematite (α- Fe2O3 ) maghemite (δ- Fe2O3 ) or magnetite (Fe3O4) in oxygen-depleted...ferric hydroxides that belong to a family of minerals known as layered double hydroxides ( LDH ). Its general formula is [FeII(6-x) FeIIIx (OH)12]x+[Ax...of ferrous and ferric hydroxides that belong to a family of minerals known as layered double hydroxides ( LDH ). Its general formula is [FeII (6-x) FeIII

Novel Nano Boehmite prepared by Solvothermal reaction of aluminum hydroxide gel in Monoethanolamine

NASA Astrophysics Data System (ADS)

Ohta, Yasuhiro; Hayakawa, Tomokatsu; Inomata, Tomohiko; Ozawa, Tomohiro; Masuda, Hideki

2017-07-01

Solvothermal reaction of aluminum hydroxide gel (AHG) in monoethanolamine (MEA) was studied at several temperatures (100, 120, 150, and 200 °C) in several reaction times (2, 3, 4, 5, 6, and 13 h). The reaction product prepared at a low temperature of 120 °C in the reaction time more than 6 h gave a blue photoluminescence nanoboehmite intercalated with monoethanolamine derivatives (BM-MEA) in the colloidal solution, which showed a photoluminescence emission centered at 420 nm with an excitation of 360 nm. The powdery samples recovered from the reaction products were characterized by using elemental analysis, XRD analysis, IR spectroscopy, thermogravimetric (TG)-DTA, 13C and 27Al CP/MAS NMR spectroscopies, N2 gas adsorption/desorption isotherm, SEM and TEM images, and photoluminescence spectroscopy. The X-ray diffraction revealed that the basal space in BM-MEA was expanded from 0.61 to 1.2 nm by intercalation of MEA derivatives to boehmite, and the IR and 13C CP/MAS NMR spectra determined that the intercalated MEA derivatives are protonated- and carbamate-substituted MEAs, which are formed in the layers through a covalent bond with Al-OH groups on boehmite surface. The empirical formula of BM-MEA was estimated to be AlO(OH)0.82(OCH2CH2NH3 +)0.05(OCH2CH2NHCOO-)0.13 on the basis of the elemental TG-DTA and IR spectral analyses. We discuss the reaction mechanism of a unique blue photoluminescence BM-MEA formed by proceeding in CO2-H2O-alkanolamine system.

Automated solid-phase extraction of phenolic acids using layered double hydroxide-alumina-polymer disks.

PubMed

Ghani, Milad; Palomino Cabello, Carlos; Saraji, Mohammad; Manuel Estela, Jose; Cerdà, Víctor; Turnes Palomino, Gemma; Maya, Fernando

2018-01-26

The application of layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks for solid-phase extraction is reported for the first time. Al 2 O 3 is embedded in a polymer matrix followed by an in situ metal-exchange process to obtain a layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disk with excellent flow-through properties. The extraction performance of the prepared disks is evaluated as a proof of concept for the automated extraction using sequential injection analysis of organic acids (p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid) following an anion-exchange mechanism. After the solid-phase extraction, phenolic acids were quantified by reversed-phase high-performance liquid chromatography with diode-array detection using a core-shell silica-C18 stationary phase and isocratic elution (acetonitrile/0.5% acetic acid in pure water, 5:95, v/v). High sensitivity and reproducibility were obtained with limits of detection in the range of 0.12-0.25 μg/L (sample volume, 4 mL), and relative standard deviations between 2.9 and 3.4% (10 μg/L, n = 6). Enrichment factors of 34-39 were obtained. Layered double hydroxide-Al 2 O 3 -polymer mixed-matrix disks had an average lifetime of 50 extractions. Analyte recoveries ranged from 93 to 96% for grape juice and nonalcoholic beer samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An experimental study on the preparation of tochilinite-originated intercalation compounds comprised of Fe 1-xS host layers and various kinds of guest layers

NASA Astrophysics Data System (ADS)

Peng, Yiya; Xi, Guangcheng; Zhong, Chang; Wang, Linping; Lu, Jun; Sun, Ximeng; Zhu, Lu; Han, Qikun; Chen, Lin; Shi, Lei; Sun, Mei; Li, Qianrong; Yu, Min; Yin, Mingwen

2009-08-01

Tochilinite represents a mineral group of ordered mixed-layer structures containing alternating Fe 1-xS layers with mackinawite-like structure and metal hydroxide layers with Mg(OH) 2-like structure. In this article, we report the preparation of a series of tochilinite-originated (or Fe 1-xS-based) intercalation compounds (ICs). According to their preparation procedures, these ICs can be divided into four kinds. The first kind of IC was sodium tochilinite (Na-tochilinite), which was prepared by the hydrothermal reaction of metallic Fe particles with concentrated Na 2S·9H 2O aqueous solutions. The hydroxide layer of the Na-tochilinite was a mixed hydroxide of Na + ions along with a certain amount of Fe 2+ ions. When the hydroxide layer of the Na-tochilinite completely dissolved in aqueous solutions, a Fe-deficient mackinawite-like phase Fe 1-xS was obtained, which was probably an electron-deficient p-type conductor. The second kind of ICs was prepared by 'low-temperature direct intercalation in aqueous solutions, using Na-tochilinite as a parental precursor. When the Na-tochilinite was ultrasonicated in aqueous solutions containing Lewis basic complexing agents (like NH 3, N 2H 4, 2,2'-bipyridine (bipy), and 1,10-phenanthroline (phen)), the Na + ions of the Na-tochilinite were removed and the Lewis basic complexing agents entered the hydroxide layer of the Na-tochilinite and became coordinated with the Fe 2+ ions, and the second kind of ICs was thus produced. The second kind of ICs includes NH 3 IC, N 2H 4 IC, N 2H 4-NH 3 IC, [Fe(bipy) 3] 2+-containing IC and [Fe(phen) 3] 2+-containing IC. The third kind of ICs, which includes NH 3 IC, N 2H 4-NH 3 IC and N 2H 4-LiOH (NaOH) IC, was prepared by the hydrothermal reaction of metallic Fe particles with (NH 4) 2S aqueous solution, S (elemental) + N 2H 4·H 2O aqueous solution, and S + N 2H 4·H 2O + LiOH (NaOH) aqueous solution, respectively. The third kind of ICs has a close relationship with the second kind of ICs both in composition and structure. The fourth kind of ICs was prepared by the oxidation and reduction of some of the N 2H 4-containing ICs mentioned above, which include N 2H 2 (diazene or diimide) IC, N 2 (dinitrogen) IC and NH 3 IC. The N 2H 2 IC was prepared by mild air oxidation of the N 2H 4-LiOH IC. The N 2 IC was prepared by strong air oxidation of the N 2H 4-LiOH IC, however, we have not been able to separate the pure phase N 2 IC. Hydrothermal reduction of the N 2H 4 IC made by the direct intercalation method in strong reducing environment by H 2S + Fe (metal) led to the production of the NH 3 IC of the fourth kind of ICs. The NH 3 ICs prepared by the three methods had similar compositions and structures. As almost all the ICs reported in this paper were extremely sensitive both to air and to the electron beam, they were mainly characterized by XRD. The properties and interrelationships (or mutual transformations) of the Fe 1-xS-based ICs revealed novel chemistry occurring in the sub-nanoscopic space between the micrometer- to nanometer-sized electron-deficient Fe 1-xS layers. An important finding of this novel chemistry was that the Fe 1-xS-based ICs tended to oxidize or reduce the intercalated species when the redox state of their environments varied. The results of our experiments potentially have many cosmochemical implications. The most important implication is that our experimental results, along with previous studies, strongly suggested that some of the ammonium salts, ammonia and carbonates existing in the matrix of the CM carbonaceous chondrites may have been formed by abiotic reactions employing molecular nitrogen as the nitrogen source and carbon monoxide as the carbon source and iron sulfide and/or iron hydroxide as catalysts.

Chemical treatment of wastewater from flue gas desulphurisation

NASA Astrophysics Data System (ADS)

Pasiecznik, Iwona; Szczepaniak, Włodzimierz

2017-11-01

The article presents results of laboratory tests of removing boron and arsenium from non-ideal solutions using double-layered magnesium/aluminium hydroxides (Mg/Al Double-Layered Hydroxide - DLH) produced with nitrate-chloride method. In research, wastewater from an installation for flue gas desulfurization was examined. Double-layered hydroxides are perfect absorbents for anionic compounds. The research proved high effectiveness of preparation with reference to arsenium, as well as confirmed the effect of presence of sulfatic and arsenate ions on the effectiveness of boron removal. On the basis of research on absorption kinetics a theoretical dose of DLH/NO3-Cl/M preparation was calculated and compared with a dose that ensures emimination of boron below the limit standarized by the national regulations. Application of double-layered magnesium/aluminium hydroxides for boron elimination from industrial wastewater requires significantly higher doses of preparation than those calculated in model investigations. It is due to the priority of removal of multivalent ions, such as sulfatic, arsenate or phosphate ions, by DLH/NO3-Cl/M.

Evaluation of layered zinc hydroxide nitrate and zinc/nickel double hydroxide salts in the removal of chromate ions from solutions

NASA Astrophysics Data System (ADS)

de Oliveira, Henrique Bortolaz; Wypych, Fernando

2016-11-01

Layered zinc hydroxide nitrate (ZnHN) and Zn/Ni layered double hydroxide salts were synthesized and used to remove chromate ions from solutions at pH 8.0. The materials were characterized by many instrumental techniques before and after chromate ion removal. ZnHN decomposed after contact with the chromate solution, whereas the layered structure of Zn/Ni hydroxide nitrate (Zn/NiHN) and Zn/Ni hydroxide acetate (Zn/NiHA) remained their layers intact after the topotactic anionic exchange reaction, only changing the basal distances. ZnHN, Zn/NiHN, and Zn/NiHA removed 210.1, 144.8, and 170.1 mg of CrO42-/g of material, respectively. Although the removal values obtained for Zn/NiHN and Zn/NiHA were smaller than the values predicted for the ideal formulas of the solids (194.3 and 192.4 mg of CrO42-/g of material, respectively), the measured capacities were higher than the values achieved with many materials reported in the literature. Kinetic experiments showed the removal reaction was fast. To facilitate the solid/liquid separation process after chromium removal, Zn/Ni layered double hydroxide salts with magnetic supports were also synthesized, and their ability to remove chromate was evaluated.

Multiple and configurable optical logic systems based on layered double hydroxides and chromophore assemblies.

PubMed

Shi, Wenying; Fu, Yi; Li, Zhixiong; Wei, Min

2015-01-14

Multiple and configurable fluorescence logic gates were fabricated via self-assembly of layered double hydroxides and various chromophores. These logic gates were operated by observation of different emissions with the same excitation wavelength, which achieve YES, NOT, AND, INH and INHIBIT logic operations, respectively.

Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors

PubMed Central

Wang, Xianfen; Kajiyama, Satoshi; Iinuma, Hiroki; Hosono, Eiji; Oro, Shinji; Moriguchi, Isamu; Okubo, Masashi; Yamada, Atsuo

2015-01-01

High-power Na-ion batteries have tremendous potential in various large-scale applications. However, conventional charge storage through ion intercalation or double-layer formation cannot satisfy the requirements of such applications owing to the slow kinetics of ion intercalation and the small capacitance of the double layer. The present work demonstrates that the pseudocapacitance of the nanosheet compound MXene Ti2C achieves a higher specific capacity relative to double-layer capacitor electrodes and a higher rate capability relative to ion intercalation electrodes. By utilizing the pseudocapacitance as a negative electrode, the prototype Na-ion full cell consisting of an alluaudite Na2Fe2(SO4)3 positive electrode and an MXene Ti2C negative electrode operates at a relatively high voltage of 2.4 V and delivers 90 and 40 mAh g−1 at 1.0 and 5.0 A g−1 (based on the weight of the negative electrode), respectively, which are not attainable by conventional electrochemical energy storage systems. PMID:25832913

Evaluation of layered zinc hydroxide nitrate and zinc/nickel double hydroxide salts in the removal of chromate ions from solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bortolaz de Oliveira, Henrique; Wypych, Fernando, E-mail: wypych@ufpr.br

Layered zinc hydroxide nitrate (ZnHN) and Zn/Ni layered double hydroxide salts were synthesized and used to remove chromate ions from solutions at pH 8.0. The materials were characterized by many instrumental techniques before and after chromate ion removal. ZnHN decomposed after contact with the chromate solution, whereas the layered structure of Zn/Ni hydroxide nitrate (Zn/NiHN) and Zn/Ni hydroxide acetate (Zn/NiHA) remained their layers intact after the topotactic anionic exchange reaction, only changing the basal distances. ZnHN, Zn/NiHN, and Zn/NiHA removed 210.1, 144.8, and 170.1 mg of CrO{sub 4}{sup 2−}/g of material, respectively. Although the removal values obtained for Zn/NiHN andmore » Zn/NiHA were smaller than the values predicted for the ideal formulas of the solids (194.3 and 192.4 mg of CrO{sub 4}{sup 2−}/g of material, respectively), the measured capacities were higher than the values achieved with many materials reported in the literature. Kinetic experiments showed the removal reaction was fast. To facilitate the solid/liquid separation process after chromium removal, Zn/Ni layered double hydroxide salts with magnetic supports were also synthesized, and their ability to remove chromate was evaluated. - Highlights: • Zinc hydroxide nitrate and Zn/Ni hydroxide nitrate or acetate were synthesized. • The interlayer anions were replaced by chromate anions at pH=8.0. • Only Zn/Ni hydroxide nitrate or acetate have the structure preserved after exchange. • Fast exchange reaction and high capacity of chromate removal were observed. • Magnetic materials were obtained to facilitate the solids removal the from solutions.« less

A molecular model for proflavine-DNA intercalation.

PubMed Central

Neidle, S; Pearl, L H; Herzyk, P; Berman, H M

1988-01-01

A molecular model has been derived for the intercalation of proflavine into the CpG site of the decamer duplex of d(GATACGATAC). The starting geometry of the intercalation site was taken from previous crystallographic studies on the d(CpG)-proflavine complex, and molecular mechanics used to obtain a stereochemically acceptable structure. This has widened grooves compared to standard A- or B- double helices, as well as distinct conformational, roll, twist and tilt features. PMID:3174439

Energy and structure of bonds in the interaction of organic anions with layered double hydroxide nanosheets: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Tsukanov, A. A.; Psakhie, S. G.

2016-01-01

The application of hybrid and hierarchical nanomaterials based on layered hydroxides and oxyhydroxides of metals is a swiftly progressing field in biomedicine. Layered double hydroxides (LDH) possess a large specific surface area, significant surface electric charge and biocompatibility. Their physical and structural properties enable them to adsorb various kinds of anionic species and to transport them into cells. However, possible side effects resulting from the interaction of LDH with anions of the intercellular and intracellular medium need to be considered, since such interaction can potentially disrupt ion transport, signaling processes, apoptosis, nutrition and proliferation of living cells. In the present paper molecular dynamics is used to determine the energies of interaction of organic anions (aspartic acid, glutamic acid and bicarbonate) with a fragment of layered double hydroxide Mg/Al-LDH. The average number of hydrogen bonds between the anions and the hydroxide surface and characteristic binding configurations are determined. Possible effects of LDH on the cell resulting from binding of protein fragments and replacement of native intracellular anions with delivered anions are considered.

Preparation of hippurate-zinc layered hydroxide nanohybrid and its synergistic effect with tamoxifen on HepG2 cell lines

PubMed Central

Ali, Samer Hasan Hussein Al; Al-Qubaisi, Mothanna; Hussein, Mohd Zobir; Zainal, Zulkarnain; Hakim, Muhammad Nazrul

2011-01-01

Background A new simple preparation method for a hippurate-intercalated zinc-layered hydroxide (ZLH) nanohybrid has been established, which does not need an anion-exchange procedure to intercalate the hippurate anion into ZLH interlayers. Methods The hippuric acid nanohybrid (HAN) was prepared by direct reaction of an aqueous suspension of zinc oxide with a solution of hippuric acid via a one-step method. Results The basal spacing of the nanohybrid was 21.3 Å, indicating that the hippurate anion was successfully intercalated into the interlayer space of ZLH, and arranged in a monolayer fashion with the carboxylate group pointing toward the ZLH inorganic interlayers. A Fourier transform infrared study confirmed the formation of the nanohybrid, while thermogravimetry and differential thermogravimetry analyses showed that the thermal stability of the nanohybrid was markedly enhanced. The loading of hippurate in the nanohybrid was estimated to be about 38.7% (w/w), and the release of hippurate from the nanohybrid was of a controlled manner, and therefore the resulting material was suitable for use as a controlled-release formulation. HAN has synergistic properties with tamoxifen toward a HepG2 cell line, with an IC50 value of 0.35 compared with hippurate. In the antiproliferative assay, the ratio of viable cells account for cells treated by the combination tamoxifen with HAN to untreated cells was sharply reduced from 66% to 13% after 24 and 72 hours, respectively. Conclusion The release of hippuric acid anions from HAN occurred in a controlled manner, and the resulting material is suitable for a controlled-release formulation. PMID:22163163

Efficient uranium capture by polysulfide/layered double hydroxide composites.

PubMed

Ma, Shulan; Huang, Lu; Ma, Lijiao; Shim, Yurina; Islam, Saiful M; Wang, Pengli; Zhao, Li-Dong; Wang, Shichao; Sun, Genban; Yang, Xiaojing; Kanatzidis, Mercouri G

2015-03-18

There is a need to develop highly selective and efficient materials for capturing uranium (normally as UO2(2+)) from nuclear waste and from seawater. We demonstrate the promising adsorption performance of S(x)-LDH composites (LDH is Mg/Al layered double hydroxide, [S(x)](2-) is polysulfide with x = 2, 4) for uranyl ions from a variety of aqueous solutions including seawater. We report high removal capacities (q(m) = 330 mg/g), large K(d)(U) values (10(4)-10(6) mL/g at 1-300 ppm U concentration), and high % removals (>95% at 1-100 ppm, or ∼80% for ppb level seawater) for UO2(2+) species. The S(x)-LDHs are exceptionally efficient for selectively and rapidly capturing UO2(2+) both at high (ppm) and trace (ppb) quantities from the U-containing water including seawater. The maximum adsorption coeffcient value K(d)(U) of 3.4 × 10(6) mL/g (using a V/m ratio of 1000 mL/g) observed is among the highest reported for U adsorbents. In the presence of very high concentrations of competitive ions such as Ca(2+)/Na(+), S(x)-LDH exhibits superior selectivity for UO2(2+), over previously reported sorbents. Under low U concentrations, (S4)(2-) coordinates to UO2(2+) forming anionic complexes retaining in the LDH gallery. At high U concentrations, (S4)(2-) binds to UO2(2+) to generate neutral UO2S4 salts outside the gallery, with NO3(-) entering the interlayer to form NO3-LDH. In the presence of high Cl(-) concentration, Cl(-) preferentially replaces [S4](2-) and intercalates into LDH. Detailed comparison of U removal efficiency of S(x)-LDH with various known sorbents is reported. The excellent uranium adsorption ability along with the environmentally safe, low-cost constituents points to the high potential of S(x)-LDH materials for selective uranium capture.

In Situ Clay Formation: Evaluation of a Proposed New Technology for Stable Containment Barriers

DTIC Science & Technology

2004-03-01

situ layered double hydroxide precipitation........... 23 4.2.1 Solution preparation and column mixing...22 Table 4.2 Summary of in situ precipitation of layered double hydroxide (LDH...effect on permeability for the smallest volume precipitated is sheet silicates or layered -clay phases (hereafter called “clays”). In natural

Advanced biohybrid materials based on nanoclays for biomedical applications

NASA Astrophysics Data System (ADS)

Ruiz-Hitzky, Eduardo; Darder, Margarita; Wicklein, Bernd; Fernandes, Francisco M.; Castro-Smirnov, Fidel A.; Martín del Burgo, M. Angeles; del Real, Gustavo; Aranda, Pilar

2012-10-01

Bio-nanohybrids prepared by assembling natural polymers (polysaccharides, proteins, nucleic acids, etc) to nanosized silicates (nanoclays) and related solids (layered double hydroxides, LDHs) give rise to the so-called bionanocomposites constituting a group of biomaterials with potential applications in medicine. In this way, biopolymers, including chitosan, pectin, alginate, xanthan gum, ι-carrageenan, gelatin, zein, and DNA, as well as phospholipids such as phosphatidylcholine, have been incorporated in layered host matrices by means of ion-exchange mechanisms producing intercalation composites. Also bio-nanohybrids have been prepared by the assembly of diverse bio-polymers with sepiolite, a natural microfibrous magnesium silicate, in this case through interactions affecting the external surface of this silicate. The properties and applications of these resulting biomaterials as active phases of ion-sensors and biosensors, for potential uses as scaffolds for tissue engineering, drug delivery, and gene transfection systems, are introduced and discussed in this work. It is also considered the use of synthetic bionanocomposites as new substrates to immobilize microorganisms, as for instance to bind Influenza virus particles, allowing their application as effective low-cost vaccine adjuvants and carriers.

Synthesis of porous and nonporous ZnO nanobelt, multipod, and hierarchical nanostructure from Zn-HDS

NASA Astrophysics Data System (ADS)

Jang, Eue-Soon; Won, Jung-Hee; Kim, Young-Woon; Cheng, Zhen; Choy, Jin-Ho

2010-08-01

Zn based hydroxide double salts (Zn-HDS) with an interlayer spacing of 20 Å was produced by dissolving dumbbell-like ZnO crystal. The resulting Zn-HDS with a ribbon-like shape has a suitable morphology to explore the remarkably mild procedure for synthesis of ZnO nanobelts. We found that the intercalated water molecules into the Zn-HDS could play a key role in the ZnO nanobelts porosity. The nonporous ZnO nanobelts were successfully synthesized from the Zn-HDS by soft-solution process at 95 °C through mild dehydration agent as Na 2CO 3. As-synthesized ZnO nanobelts were grown along not only the [0 1 -1 0], but also the [2 -1 -1 0]. On the other hand, the porous ZnO nanobelts were obtained from the Zn-HDS by calcinations at 200 and 400 °C. In addition, flower-like ZnO multipod and hierarchical nanostructures were produced from the Zn-HDS by using of strong dehydration agent (NaOH) through hydrothermal reaction at 150 and 230 °C.

Nanosheets of oxides and hydroxides: Ultimate 2D charge-bearing functional crystallites.

PubMed

Ma, Renzhi; Sasaki, Takayoshi

2010-12-01

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.

DOUBLE SHELL TANK (DST) HYDROXIDE DEPLETION MODEL FOR CARBON DIOXIDE ABSORPTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

OGDEN DM; KIRCH NW

2007-10-31

This document generates a supernatant hydroxide ion depletion model based on mechanistic principles. The carbon dioxide absorption mechanistic model is developed in this report. The report also benchmarks the model against historical tank supernatant hydroxide data and vapor space carbon dioxide data. A comparison of the newly generated mechanistic model with previously applied empirical hydroxide depletion equations is also performed.

Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

PubMed

Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

2014-06-25

We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

Electric and dielectric behavior of copper-chromium layered double hydroxide intercalated with dodecyl sulfate anions using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Elhatimi, Wafaa; Bouragba, Fatima Zahra; Lahkale, Redouane; Sadik, Rachid; Lebbar, Nacira; Siniti, Mostapha; Sabbar, Elmouloudi

2018-05-01

The Cu2Cr-DS-LDH hybrid was successfully prepared by the anion exchange method at room temperature. The structure, the chemical composition and the physico-chemical properties of the sample were determined using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and inductively coupled plasma (ICP). In this work, the electrical and dielectric properties investigated are determined using impedance spectroscopy (IS) in a frequency range of 1 Hz to 1 MHz. Indeed, the Nyquist diagram modelized by an electrical equivalent circuit showed three contributions attributed respectively to the polarization of grains, grains boundaries and interface electrode-sample. This modelization allowed us to determine the intrinsic electrical parameters of the hybrid (resistance, pseudo-capacitance and relaxation time). The presence of the non-Debye relaxation phenomena was confirmed by the frequency analysis of impedance. Moreover, the evolution of the alternating current conductivity (σac) studied obeys the double power law of Jonscher. The ionic conduction of this material was generated through a jump movement by translation of the charge carriers. As for the dielectric behavior of the material, the evolution of dielectric constant as a function of frequency shows relatively high values in a frequency range between 10 Hz and 1 KHz. The low values of the loss tangent obtained in this frequency zone can valorize this LDH hybrid.

Layered double hydroxide stability. 2. Formation of Cr(III)-containing layered double hydroxides directly from solution

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.; Jiang, J.; Lou, S.; Yarberry, F.

1999-01-01

Solutions containing divalent metal [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+] chlorides and CrCl3 6H2O were titrated with NaOH to yield, for M(II) = Zn, Co, and Ni, hydrotalcite-like layered double hydroxides (LDHs), [[M(II)]1-z[Cr(III)]z(OH)2][Cl]z yH2O, in a single step, without intermediate formation of chromium hydroxide. Analysis of the resultant titration curves yields solubility constants for these compounds. These are in the order Zn < Ni approximately Co, with a clear preference for formation of the phase with z = 1/3. With Mg2+ as chloride, titration gives a mixture of Cr(OH)3 and Mg(OH)2, but the metal sulfates give Mg2Cr(OH)6 1/2(SO4) by a two-step process. Titrimetric and spectroscopic evidence suggests short-range cation order in the one-step LDH systems.

Layered assembly of graphene oxide and Co-Al layered double hydroxide nanosheets as electrode materials for supercapacitors.

PubMed

Wang, Lei; Wang, Dong; Dong, Xin Yi; Zhang, Zhi Jun; Pei, Xian Feng; Chen, Xin Jiang; Chen, Biao; Jin, Jian

2011-03-28

An innovative strategy of fabricating electrode material by layered assembling two kinds of one-atom-thick sheets, carboxylated graphene oxide (GO) and Co-Al layered double hydroxide nanosheet (Co-Al LDH-NS) for the application as a pseudocapacitor is reported. The Co-Al LDH-NS/GO composite exhibits good energy storage properties.

Stereochemical model for proflavin intercalation in A-DNA.

PubMed Central

Alden, C J; Arnott, S

1977-01-01

Linked-atom molecular modelling was employed to determine the steric and torsional requirements for intercalation of proflavine into a double-stranded region of DNA compatible with adjacent regions of cohelical A-DNA. The optimum intercalation conformation is characterized by the dihedral angles xi and psi becoming trans, with all sugars retaining the characteristics C3'-endo pucker. This extended conformation results in virtually no helical unwinding, suggesting it may be an appropriate model for an intercalative intermediary in mutagenesis by virtue of its similarity to standard helical DNA. PMID:593890

Sustained release formulation of an anti-tuberculosis drug based on para-amino salicylic acid-zinc layered hydroxide nanocomposite.

PubMed

Saifullah, Bullo; Hussein, Mohd Zobir; Hussein-Al-Ali, Samer Hasan; Arulselvan, Palanisamy; Fakurazi, Sharida

2013-04-20

Tuberculosis (TB), is caused by the bacteria, Mycobacterium tuberculosis and its a threat to humans since centuries. Depending on the type of TB, its treatment can last for 6-24 months which is a major cause for patients non-compliance and treatment failure. Many adverse effects are associated with the currently available TB medicines, and there has been no new anti-tuberculosis drug on the market for more than 50 year, as the drug development is very lengthy and budget consuming process.Development of the biocompatible nano drug delivery systems with the ability to minimize the side effects of the drugs, protection of the drug from enzymatic degradation. And most importantly the drug delivery systems which can deliver the drug at target site would increase the therapeutic efficacy. Nanovehicles with their tendency to release the drug in a sustained manner would result in the bioavalibilty of the drugs in the body for a longer period of time and this would reduce the dosing frequency in drug administration. The biocompatible nanovehicles with the properties like sustained release of drug of the target site, protection of the drug from physio-chemical degradation, reduction in dosing frequency, and prolong bioavailability of drug in the body would result in the shortening of the treatment duration. All of these factors would improve the patient compliance with chemotherapy of TB. An anti-tuberculosis drug, 4-amino salicylic acid (4-ASA) was successfully intercalated into the interlamellae of zinc layered hydroxide (ZLH) via direct reaction with zinc oxide suspension. The X-ray diffraction patterns and FTIR analyses indicate that the molecule was successfully intercalated into the ZLH interlayer space with an average basal spacing of 24 Å. Furthermore, TGA and DTG results show that the drug 4-ASA is stabilized in the interlayers by electrostatic interaction. The release of 4-ASA from the nanocomposite was found to be in a sustained manner. The nanocomposite treated with normal 3T3 cells shows it reduces cell viability in a dose- and time-dependent manner. Sustained release formulation of the nanocomposite, 4-ASA intercalated into zinc layered hydroxides, with its ease of preparation, sustained release of the active and less-toxic to the cell is a step forward for a more patient-friendly chemotherapy of Tuberculosis.

Sustained release formulation of an anti-tuberculosis drug based on para-amino salicylic acid-zinc layered hydroxide nanocomposite

PubMed Central

2013-01-01

Background Tuberculosis (TB), is caused by the bacteria, Mycobacterium tuberculosis and its a threat to humans since centuries. Depending on the type of TB, its treatment can last for 6–24 months which is a major cause for patients non-compliance and treatment failure. Many adverse effects are associated with the currently available TB medicines, and there has been no new anti-tuberculosis drug on the market for more than 50 year, as the drug development is very lengthy and budget consuming process. Development of the biocompatible nano drug delivery systems with the ability to minimize the side effects of the drugs, protection of the drug from enzymatic degradation. And most importantly the drug delivery systems which can deliver the drug at target site would increase the therapeutic efficacy. Nanovehicles with their tendency to release the drug in a sustained manner would result in the bioavalibilty of the drugs in the body for a longer period of time and this would reduce the dosing frequency in drug administration. The biocompatible nanovehicles with the properties like sustained release of drug of the target site, protection of the drug from physio-chemical degradation, reduction in dosing frequency, and prolong bioavailability of drug in the body would result in the shortening of the treatment duration. All of these factors would improve the patient compliance with chemotherapy of TB. Result An anti-tuberculosis drug, 4-amino salicylic acid (4-ASA) was successfully intercalated into the interlamellae of zinc layered hydroxide (ZLH) via direct reaction with zinc oxide suspension. The X-ray diffraction patterns and FTIR analyses indicate that the molecule was successfully intercalated into the ZLH interlayer space with an average basal spacing of 24 Å. Furthermore, TGA and DTG results show that the drug 4-ASA is stabilized in the interlayers by electrostatic interaction. The release of 4-ASA from the nanocomposite was found to be in a sustained manner. The nanocomposite treated with normal 3T3 cells shows it reduces cell viability in a dose- and time-dependent manner. Conclusions Sustained release formulation of the nanocomposite, 4-ASA intercalated into zinc layered hydroxides, with its ease of preparation, sustained release of the active and less-toxic to the cell is a step forward for a more patient-friendly chemotherapy of Tuberculosis. PMID:23601852

Synthesis, characterization, and evaluation of simple aluminum-based adsorbents for fluoride removal from drinking water.

PubMed

Du, Junyi; Sabatini, David A; Butler, Elizabeth C

2014-04-01

Simple aluminum (hydr)oxides and layered double hydroxides were synthesized using common chemicals and equipment by varying synthesis temperature, concentrations of extra sulfate and citrate, and metal oxide amendments. Aluminum (hydr)oxide samples were aged at either 25 or 200°C during synthesis and, in some cases, calcined at 600 °C. Despite yielding increased crystallinity and mineral phase changes, higher temperatures had a generally negative effect on fluoride adsorption. Addition of extra sulfate during synthesis of aluminum (hydr)oxides led to significantly higher fluoride adsorption capacity compared to aluminum (hydr)oxides prepared with extra citrate or no extra ligands. X-ray diffraction results suggest that extra sulfate led to the formation of both pseudoboehmite (γ-AlOOH) and basaluminite (Al4SO4(OH)10⋅4H2O) at 200 °C; energy dispersive X-ray spectroscopy confirmed the presence of sulfur in this solid. Treatment of aluminum (hydr)oxides with magnesium, manganese, and iron oxides did not significantly impact fluoride adsorption. While layered double hydroxides exhibited high maximum fluoride adsorption capacities, their adsorption capacities at dissolved fluoride concentrations close to the World Health Organization drinking water guideline of 1.5 mg L(-1) were much lower than those for the aluminum (hydr)oxides. Copyright © 2013 Elsevier Ltd. All rights reserved.

Structural Differentiation between Layered Single (Ni) and Double Metal Hydroxides (Ni–Al LDHs) Using Wavelet Transformation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siebecker, Matthew G.; Sparks, Donald L.

2017-09-07

Layered double hydroxides (LDHs) are anionic clays important in disciplines such as environmental chemistry, geochemistry, and materials science. Developments in signal processing of extended X-ray absorption fine structure (EXAFS) data, such as wavelet transformation (WT), have been used to identify transition metals and Al present in the hydroxide sheets of LDHs. The WT plots of LDHs should be distinct from those of isostructural single metal hydroxides. However, no direct comparison of these minerals appears in the literature using WT. This work systematically analyzes a suite of Ni-rich mineral standards, including Ni–Al LDHs, single metal Ni hydroxides, and Ni-rich silicates usingmore » WT. The results illustrate that the WT plots for α-Ni(OH)2 and Ni–Al LDHs are often indistinguishable from each other, with similar two-component plots for the different mineral types. This demonstrates that the WT of the first metal shell often cannot be used to differentiate an LDH from a single metal hydroxide. Interlayer anions adsorbed to the hydroxide sheet of α-Ni(OH)2 affect the EXAFS spectra and are not visible in the FT but are clearly resolved and discrete in the WT.« less

Zn- and Co-based layered double hydroxides: prediction of the a parameter from the fraction of trivalent cations and vice versa

PubMed Central

Richardson, Ian G.

2013-01-01

A recently proposed method to calculate the a parameter of the unit cell of layered double hydroxides from the fraction of trivalent cations is extended to Zn- and Co-based phases. It is shown to be useful as a sanity test for extant and future structure determinations and computer-simulation studies. PMID:23873067

Magnetic Properties of nickel hydroxides layers 30A apart obtained by intercalation with dodecyl sulfate ion

NASA Astrophysics Data System (ADS)

Shmavonyan, Gagik; Zadoyan, Ovsanna

2013-03-01

Magnetic systems with reduced dimensionality make good test beds for checks on theoretical models. Here, changes in the nature of magnetic ordering in quasi-2d system of layered Ni hydroxides (LH-Ni-) with variations in the interlayer spacing c are investigated. Magnetic properties of LH-Ni-DS with c ~ 30 A° synthesized by intercalating dodecyl sulfate ion, (C12H25OSO3)- between the layers are compared with those of LH-Ni-Ac (c ~ 8.5 A°) containing the acetate (Ac) ligand. Measurements included those of magnetization M vs. T and H, ac susceptibilities (f = 0.1 Hz - 1000 Hz) and EMR (Electron Magnetic Resonance) spectra at 9.28 GHz. Results show that just like LH-Ni-Ac, LH-Ni-DS also orders ferromagnetically but with Tc ~ 23 Kabout 45 % largerthanT c 16 Kreportedfor LH-Ni-Ac.. In EMR studies, linewidth is strongly temperature-dependent, decreasing with decreasing T from 300 K, reaching a minimum near 45 K and then increasing sharply for T < 45 K, the latter due to short range magnetic ordering. These results differ with the model of Drillon et al in which interlayer dipolar interaction between clusters of correlated spins in the layers yields TC nearly independent of c. Roles of magnetic anisotropy and exchange constants in determining TC in the LH-Ni systems is discussed.

Mechanisms of small molecule–DNA interactions probed by single-molecule force spectroscopy

PubMed Central

Almaqwashi, Ali A.; Paramanathan, Thayaparan; Rouzina, Ioulia; Williams, Mark C.

2016-01-01

There is a wide range of applications for non-covalent DNA binding ligands, and optimization of such interactions requires detailed understanding of the binding mechanisms. One important class of these ligands is that of intercalators, which bind DNA by inserting aromatic moieties between adjacent DNA base pairs. Characterizing the dynamic and equilibrium aspects of DNA-intercalator complex assembly may allow optimization of DNA binding for specific functions. Single-molecule force spectroscopy studies have recently revealed new details about the molecular mechanisms governing DNA intercalation. These studies can provide the binding kinetics and affinity as well as determining the magnitude of the double helix structural deformations during the dynamic assembly of DNA–ligand complexes. These results may in turn guide the rational design of intercalators synthesized for DNA-targeted drugs, optical probes, or integrated biological self-assembly processes. Herein, we survey the progress in experimental methods as well as the corresponding analysis framework for understanding single molecule DNA binding mechanisms. We discuss briefly minor and major groove binding ligands, and then focus on intercalators, which have been probed extensively with these methods. Conventional mono-intercalators and bis-intercalators are discussed, followed by unconventional DNA intercalation. We then consider the prospects for using these methods in optimizing conventional and unconventional DNA-intercalating small molecules. PMID:27085806

Anion-exchange membranes derived from quaternized polysulfone and exfoliated layered double hydroxide for fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Wan; Liang, Na; Peng, Pai

2017-02-15

Layered double hydroxides (LDH) are prepared by controlling urea assisted homogeneous precipitation conditions. Morphology and crystallinity of LDHs are confirmed by X-ray diffraction and scanning electron microscope. After LDHs are incorporated into quaternized polysulfone membranes, transmission electron microscope is used to observe the exfoliated morphology of LDH sheets in the membranes. The properties of the nanocomposite membranes, including water uptake, swelling ratio, mechanical property and ionic conductivity are investigated. The nanocomposite membrane containing 5% LDH sheets shows more balanced performances, exhibiting an ionic conductivity of 2.36×10{sup −2} S cm{sup −1} at 60 °C. - Graphical abstract: Anion-exchange membrane based onmore » quaternized polysulfone and exfoliated layered double hydroxide is optically transparent and has good ionic properties.« less

Facile synthesis of nickel-cobalt double hydroxide nanosheets with high rate capability for application in supercapacitor

NASA Astrophysics Data System (ADS)

Wang, Minmin; Xue, Junying; Zhang, Fangming; Ma, Wenle; Cui, Hongtao

2015-02-01

In this work, nickel-cobalt double hydroxide nanosheets with high rate capability are prepared by a facile epoxide precipitation route. The synthetic procedure includes an oxidization step using ammonium persulfate as oxidant and a precipitation step using propylene oxide as precipitation agent. As shown in the results of electrochemical characterization, high specific capacitance of 2548 F g-1 for this material can be obtained at current density of 0.9 A g-1 in aqueous solution of 3 mol L-1 KOH. It is surprising to notice that the capacitance of material still remains 1587 F g-1 at high current density of 35.7 A g-1. These results demonstrate that the as-prepared nickel-cobalt double hydroxide nanosheets are promising electrode material for supercapacitor application as a primary power source.

Morphologies, Preparations and Applications of Layered Double Hydroxide Micro-/Nanostructures

PubMed Central

Kuang, Ye; Zhao, Lina; Zhang, Shuai; Zhang, Fazhi; Dong, Mingdong; Xu, Sailong

2010-01-01

Layered double hydroxides (LDHs), also well-known as hydrotalcite-like layered clays, have been widely investigated in the fields of catalysts and catalyst support, anion exchanger, electrical and optical functional materials, flame retardants and nanoadditives. This feature article focuses on the progress in micro-/nanostructured LDHs in terms of morphology, and also on the preparations, applications, and perspectives of the LDHs with different morphologies. PMID:28883378

Determination of haloacetic acids in water using layered double hydroxides as a sorbent in dispersive solid-phase extraction followed by liquid chromatography with tandem mass spectrometry.

PubMed

Alsharaa, Abdulnaser; Sajid, Muhammad; Basheer, Chanbasha; Alhooshani, Khalid; Lee, Hian Kee

2016-09-01

In the present study, highly efficient and simple dispersive solid-phase extraction procedure for the determination of haloacetic acids in water samples has been established. Three different types of layered double hydroxides were synthesized and used as a sorbent in dispersive solid-phase extraction. Due to the interesting behavior of layered double hydroxides in an acidic medium (pH˂4), the analyte elution step was not needed; the layered double hydroxides are simply dissolved in acid immediately after extraction to release the analytes which are then directly introduced into a liquid chromatography with tandem mass spectrometry system for analysis. Several dispersive solid-phase extraction parameters were optimized to increase the extraction efficiency of haloacetic acids such as temperature, extraction time and pH. Under optimum conditions, good linearity was achieved over the concentration range of 0.05-100 μg/L with detection limits in the range of 0.006-0.05 μg/L. The relative standard deviations were 0.33-3.64% (n = 6). The proposed method was applied to different water samples collected from a drinking water plant to determine the concentrations of haloacetic acids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chitosan/zinc oxide-polyvinylpyrrolidone (CS/ZnO-PVP) nanocomposite for better thermal and antibacterial activity.

PubMed

Karpuraranjith, M; Thambidurai, S

2017-11-01

A new biopolymer based ZnO-PVP nanocomposite was successfully synthesized by single step in situ precipitation method using chitosan as biosurfactant, zinc chloride as a source material, PVP as stabilizing agent and sodium hydroxide as precipitating agent. The chemical bonding and crystalline behaviors of chitosan, zinc oxide and PVP were confirmed by FT-IR and XRD analysis. The biopolymer connected ZnO particles intercalated PVP matrix was layer and rod like structure appeared in nanometer range confirmed by HR-SEM and TEM analysis. The surface topography image of CS/ZnO-PVP nanocomposite was obtained in the average thickness of 12nm was confirmed by AFM analysis. Thermal stability of cationic biopolymer based ZnO intercalated PVP has higher stability than CS-PVP and chitosan. Consequently, antimicrobial activity of chitosan/ZnO-PVP matrix acts as a better microbial inhibition activity than PVP-ZnO nanocomposite. The obtained above results demonstrate that CS and ZnO intercalated PVP matrix has better reinforced effect than other components. Therefore, Chitosan/ZnO-PVP nanocomposite may be a promising material for the biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydroxide catalysts for lignin depolymerization

DOEpatents

Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

2017-10-17

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

Hydroxide catalysts for lignin depolymerization

DOEpatents

Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

2017-04-25

Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

Effect of carbon entrapped in Co-Al double oxides on structural restacking and electrochemical performances

NASA Astrophysics Data System (ADS)

Su, Ling-Hao; Zhang, Xiao-Gang

Co-Al layered double hydroxides (LDH) were synthesized from nitrates and sodium benzoate by direct coprecipitation, and heated at 600 °C for 3 h in argon gas flow to obtain Co-Al double oxides. The effect of carbon, created during the pyrolysis of benzoate and inserted in resulting double oxides, on structural reconstruction was investigated by X-ray diffraction, scanning electron microscope, Raman spectroscopy, and infrared spectroscopy techniques. It is horizontal arrangement rather than vertical dilayer orientation in the interlayer spacing that was adopted by benzoate. An abnormal phenomenon was found that when immersed in aqueous 6 M KOH solution in air, the double oxides restacked to Co-Al layered double hydroxides with more regular crystal than before. The reason is believed that carbon was confined in the matrix of resulting double oxides, which prevented further collapse of the layered structure. Cyclic voltammetries (CV) and constant current charge/discharge measurements reveal that the restacked Co-Al layered double hydroxide has good long-life capacitive performance with a capacitance up to 145 F g -1 even at a large current of 2 A g -1. In addition, two clear slopes in chronoampermetric test demonstrated two different diffusion coefficients, explaining the slope of about 118.4 mV in the plot of formal potential E f versus pOH.

Fluorescent vancomycin and terephthalate comodified europium-doped layered double hydroxides nanoparticles: synthesis and application for bacteria labelling

NASA Astrophysics Data System (ADS)

Sun, Jianchao; Fan, Hai; Wang, Nan; Ai, Shiyun

2014-09-01

Vancomycin (Van)- and terephthalate (TA)-comodified europium-doped layered double hydroxides (Van-TA-Eu-LDHs) nanoparticles were successfully prepared by a two-step method, in which, TA acted as a sensitizer to enhance the fluorescent property and Van was modified on the surface of LDH to act as an affinity reagent to bacteria. The obtained products were characterized by X-ray diffraction, transmission electron microscope and fluorescent spectroscopy. The results demonstrated that the prepared Van- and TA-comodified europium-doped layered double hydroxides (Van-TA-Eu-LDHs) nanoparticles with diameter of 50 nm in size showed highly efficient fluorescent property. Furthermore, due to the high affinity of Van to bacteria, the prepared Van-TA-Eu-LDHs nanoparticles showed efficient bacteria labelling by fluorescent property. The prepared nanoparticles may have wide applications in the biological fields, such as biomolecular labelling and cell imaging.

[Treatment of wastewater containing Cr(VI) by LDH synthesizing in situ].

PubMed

Chen, Tian-hu; Feng, You-liang; Xu, Hui-fang; Peng, Shu-chuan; Huang, Chuan-hui; Tang, Shu-pei

2004-03-01

The objective of this work was to investigate the efficiency and factors impacting of removal Cr(VI) from wastewater by layer double hydroxide synthesizing in situ. Principle of the method may be described as follow: Mg2+ and Al3+ hydrolysis and forms Mg/Al-LDH by adding Mg2+, Al3+ and NaOH into wastewater containing Cr(VI), Cr(VI) anions are selectively intercalated into interlayer of LDH to balance positive structural charge. While Mg2+ and Al3+ co-precipitates and forms LDH, the Cr(VI) in wastewater is removal by settle of LDH synthesizing in situ, which are confirmed by analysis of X-ray diffraction on settle and chemical analysis on aqueous. The results indicate that factors of impacting on efficiency of removal Cr(VI) include in amount of adding Mg2+ and Al3+, Mg/Al ratio, pH and concentration of Cr(VI) in wastewater. The maximal removal efficiency of Cr(VI) can be reached when pH values are between 8.5 and 9, and Mg/Al ratios are between 1:1 and 2:1, meanwhile, Mg and Al added can be taken good use of. This technology has present extraordinary efficiency of wastewater treatment.

Optical determination of the electronic coupling and intercalation geometry of thiazole orange homodimer in DNA

NASA Astrophysics Data System (ADS)

Cunningham, Paul D.; Bricker, William P.; Díaz, Sebastián A.; Medintz, Igor L.; Bathe, Mark; Melinger, Joseph S.

2017-08-01

Sequence-selective bis-intercalating dyes exhibit large increases in fluorescence in the presence of specific DNA sequences. This property makes this class of fluorophore of particular importance to biosensing and super-resolution imaging. Here we report ultrafast transient anisotropy measurements of resonance energy transfer (RET) between thiazole orange (TO) molecules in a complex formed between the homodimer TOTO and double-stranded (ds) DNA. Biexponential homo-RET dynamics suggest two subpopulations within the ensemble: 80% intercalated and 20% non-intercalated. Based on the application of the transition density cube method to describe the electronic coupling and Monte Carlo simulations of the TOTO/dsDNA geometry, the dihedral angle between intercalated TO molecules is estimated to be 81° ± 5°, corresponding to a coupling strength of 45 ± 22 cm-1. Dye intercalation with this geometry is found to occur independently of the underlying DNA sequence, despite the known preference of TOTO for the nucleobase sequence CTAG. The non-intercalated subpopulation is inferred to have a mean inter-dye separation distance of 19 Å, corresponding to coupling strengths between 0 and 25 cm-1. This information is important to enable the rational design of energy transfer systems that utilize TOTO as a relay dye. The approach used here is generally applicable to determining the electronic coupling strength and intercalation configuration of other dimeric bis-intercalators.

Interaction of Antitumor Agent Mitoxantrone with Double Helical Synthetic Polyribonucleotides Poly(G)ṡPoly(C) and Poly(I)ṡPoly(C)

NASA Astrophysics Data System (ADS)

Babayan, Yuri S.; Hakobyan, Sergey N.; Ghazaryan, Rusanna S.; Shahinyan, Mariam A.

The interaction of antitumor drug mitoxantrone (MTX) with double-stranded synthetic RNA homopolymers has been studied by means of spectroscopic (UV-Visible absorption, circular dichroism) techniques. The results show a base specificity in this interaction: the association constant with poly(G)ṡpoly(C) is higher than with poly(I)ṡpoly(C). Values of changes of the system enthalpy and entropy due to complex-formation were determined through the temperature dependence of the binding constant. Calculations show that due to the intercalation interaction of MTX, the values of changes of the system entropy and enthalpy differ from those obtained at ehtidium bromide interaction with synthetic polyribonucleotides, which shows that the intercalation interaction of MTX with double-stranded RNA significantly differs from that of ethidium bromide with RNA.

Antimycobacterial, antimicrobial, and biocompatibility properties of para-aminosalicylic acid with zinc layered hydroxide and Zn/Al layered double hydroxide nanocomposites

PubMed Central

Saifullah, Bullo; El Zowalaty, Mohamed E; Arulselvan, Palanisamy; Fakurazi, Sharida; Webster, Thomas J; Geilich, Benjamin M; Hussein, Mohd Zobir

2014-01-01

The treatment of tuberculosis by chemotherapy is complicated due to multiple drug prescriptions, long treatment duration, and adverse side effects. We report here for the first time an in vitro therapeutic effect of nanocomposites based on para-aminosalicylic acid with zinc layered hydroxide (PAS-ZLH) and zinc-aluminum layered double hydroxides (PAS-Zn/Al LDH), against mycobacteria, Gram-positive bacteria, and Gram-negative bacteria. The nanocomposites demonstrated good antimycobacterial activity and were found to be effective in killing Gram-positive and Gram-negative bacteria. A biocompatibility study revealed good biocompatibility of the PAS-ZLH nanocomposites against normal human MRC-5 lung cells. The para-aminosalicylic acid loading was quantified with high-performance liquid chromatography analysis. In summary, the present preliminary in vitro studies are highly encouraging for further in vivo studies of PAS-ZLH and PAS-Zn/Al LDH nanocomposites to treat tuberculosis. PMID:25114509

Intercalation compounds and electrodes for batteries

DOEpatents

Chiang, Yet-Ming; Sadoway, Donald R.; Jang, Young-Il; Huang, Biyan

2004-09-07

This invention concerns intercalation compounds and in particular lithium intercalation compounds which have improved properties for use in batteries. Compositions of the invention include particulate metal oxide material having particles of multicomponent metal oxide, each including an oxide core of at least first and second metals in a first ratio, and each including a surface coating of metal oxide or hydroxide that does not include the first and second metals in the first ratio formed by segregation of at least one of the first and second metals from the core. The core may preferably comprise Li.sub.x M.sub.y N.sub.z O.sub.2 wherein M and N are metal atom or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are such that a formal charge on M.sub.y N.sub.z portion of the compound is (4-x), and having a charging voltage of at least about 2.5V. The invention may also be characterized as a multicomponent oxide microstructure usable as a lithium intercalation material including a multiphase oxide core and a surface layer of one material, which is a component of the multiphase oxide core, that protects the underlying intercalation material from chemical dissolution or reaction. In a particular preferred example the multicomponent oxide may be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions, having an orthorhombic structure, also form a part of the invention. In addition, the invention includes articles, particularly electrodes, for batteries formed from the compositions of the invention, and batteries including such electrodes. The invention further relates to a composite intercalation material comprising at least two compounds in which at least one compound has an orthorhombic structure Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2, where y is nonzero, or a mixture of orthorhombic and monoclinic Li.sub.x Al.sub.y Mn.sub.1-y O.sub.2.

Hybrid Materials Based on Magnetic Layered Double Hydroxides: A Molecular Perspective.

PubMed

Abellán, Gonzalo; Martí-Gastaldo, Carlos; Ribera, Antonio; Coronado, Eugenio

2015-06-16

Design of functional hybrids lies at the very core of synthetic chemistry as it has enabled the development of an unlimited number of solids displaying unprecedented or even improved properties built upon the association at the molecular level of quite disparate components by chemical design. Multifunctional hybrids are a particularly appealing case among hybrid organic/inorganic materials. Here, chemical knowledge is used to deploy molecular components bearing different functionalities within a single solid so that these properties can coexist or event interact leading to unprecedented phenomena. From a molecular perspective, this can be done either by controlled assembly of organic/inorganic molecular tectons into an extended architecture of hybrid nature or by intercalation of organic moieties within the empty channels or interlamellar space offered by inorganic solids with three-dimensional (MOFs, zeolites, and mesoporous hosts) or layered structures (phosphates, silicates, metal dichalcogenides, or anionic clays). This Account specifically illustrates the use of layered double hydroxides (LDHs) in the preparation of magnetic hybrids, in line with the development of soft inorganic chemistry processes (also called "Chimie Douce"), which has significantly contributed to boost the preparation hybrid materials based on solid-state hosts and subsequent development of applications. Several features sustain the importance of LDHs in this context. Their magnetism can be manipulated at a molecular level by adequate choice of constituting metals and interlayer separation for tuning the nature and extent of magnetic interactions across and between planes. They display unparalleled versatility in accommodating a broad range of anionic species in their interlamellar space that encompasses not only simple anions but chemical systems of increasing dimensionality and functionalities. Their swelling characteristics allow for their exfoliation in organic solvents with high dielectric strength, to produce two-dimensional nanosheets with atomic thickness that can be used as macromolecular building blocks in the assembly of nanocomposites. We describe how these advantageous properties turn LDHs into excellent vehicles for the preparation of multifunctional materials with increasing levels of complexity. For clarity, the reader will first find a succinct description of the most relevant aspects controlling the magnetism of LDHs followed by their use in the preparation of magnetic hybrids from a molecular perspective. This includes the intercalation anionic species of increasing nuclearity like paramagnetic mononuclear complexes, stimulus-responsive molecular guests, one- and two-dimensional coordination polymers, or even preassembled 2D networks. This approach allows us to evolve from "dual-function" materials with coexistence, for example, of magnetism and superconductivity, to smart materials in which the magnetic or structural properties of the LDH layers can be tuned by applying an external stimulus like light or temperature. We will conclude with a brief look into the promising features offered by magnetic nanocomposites based on LDHs and our views on the most promising directions to be pursued in this context.

Nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets with a 3D nanonetwork structure as supercapacitive materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Tao; Li, Ruiyi; Li, Zaijun, E-mail: zaijunli@263.net

2014-03-01

Graphical abstract: The microwave heating reflux approach was developed for the fabrication of nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets, in which ammonia and ethanol were used as the precipitator and medium for the synthesis. The obtained composite shows a 3D flowerclusters morphology with nanonetwork structure and largely enhanced supercapacitive performance. - Highlights: • The paper reported the microwave synthesis of nickel–cobalt layered double hydroxide/graphene composite. • The novel synthesis method is rapid, green, efficient and can be well used to the mass production. • The as-synthesized composite offers a 3D flowerclusters morphology with nanonetwork structure. •more » The composite offers excellent supercapacitive performance. • This study provides a promising route to design and synthesis of advanced graphene-based materials with the superiorities of time-saving and cost-effective characteristics. - Abstract: The study reported a novel microwave heating reflux method for the fabrication of nickel–cobalt layered double hydroxide ultrathin nanoflakes decorated on graphene sheets (GS/NiCo-LDH). Ammonia and ethanol were employed as precipitant and reaction medium for the synthesis, respectively. The resulting GS/NiCo-LDH offers a 3D flowerclusters morphology with nanonetwork structure. Due to the greatly enhanced rate of electron transfer and mass transport, the GS/NiCo-LDH electrode exhibits excellent supercapacitive performances. The maximum specific capacitance was found to be 1980.7 F g{sup −1} at the current density of 1 A g{sup −1}. The specific capacitance can remain 1274.7 F g{sup −1} at the current density of 15 A g{sup −1} and it has an increase of about 2.9% after 1500 cycles. Moreover, the study also provides a promising approach for the design and synthesis of metallic double hydroxides/graphene hybrid materials with time-saving and cost-effective characteristics, which can be potentially applied in the energy storage/conversion devices.« less

Spectroscopic and electrochemical studies of the interaction between oleuropein, the major bio-phenol in olives, and salmon sperm DNA

NASA Astrophysics Data System (ADS)

Mohamadi, Maryam; Afzali, Daryoush; Esmaeili-Mahani, Saeed; Mostafavi, Ali; Torkzadeh-Mahani, Masoud

2015-09-01

Interaction of oleuropein, the major bio-phenol in olive leaf and fruit, with salmon sperm double-stranded DNA was investigated by employing electronic absorption titrations, fluorescence quenching spectroscopy, competitive fluorescence spectroscopy, thermal denaturation and voltammetric studies. Titration of oleuropein with the DNA caused a hypochromism accompanied with a red shift indicating an intercalative mode of interaction. Binding constant of 1.4 × 104 M-1 was obtained for this interaction. From the curves of fluorescence titration of oleuropein with the DNA, binding constant and binding sites were calculated to be 8.61 × 103 M-1 and 1.05, respectively. Competitive studies with ethidium bromide (a well-known DNA intercalator) showed that the bio-phenol could take the place of ethidium bromide in the DNA intercalation sites. The interaction of oleuropein with DNA was also studied electrochemically. In the presence of the DNA, the anodic and cathodic peak currents of oleuropein decreased accompanied with increases in peak-to-peak potential separation and formal potential, indicating the intercalation of oleuropein into the DNA double helix. Moreover, melting temperature of the DNA was found to increase in the presence of oleuropein, indicating the stabilization of the DNA double helix due to an intercalative interaction.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Molecular dynamics in aluminum layered double hydroxides as studied by 1H T1ρ NMR measurements

NASA Astrophysics Data System (ADS)

Vyalikh, Anastasia; Wang, De-Yi; Wagenknecht, Udo; Heinrich, Gert; Scheler, Ulrich

2011-06-01

Proton dynamics in pristine and organically-modified layered double hydroxide has been studied by 1H T1ρ. Inverse Laplace transform with spectral resolution results in a correlation of T1ρ and chemical shift. In LDH two contributions are resolved. They are assigned to the metal hydroxides, forming the LDH sheets (4-8 ms), and mobile interlayer water (2 ms). Apparent T1ρ values of OH-protons in surfactant-modified LDH are different in dodecylbenzenesulfonate- (SDBS) and sodium octasulfonate- (C8) modified LDH. This difference is explained by the presence of water in LDH-SDBS. The effects of spin diffusion have been studied by performing 2D 1H RFDR in the LDH-SDBS.

Cu sbnd Al sbnd Fe layered double hydroxides with CO32- and anionic surfactants with different alkyl chains in the interlayer

NASA Astrophysics Data System (ADS)

Trujillano, Raquel; Holgado, María Jesús; González, José Luis; Rives, Vicente

2005-08-01

Layered double hydroxides (LDHs), with the hydrotalcite-like structure containing Cu(II), Al(III) and Fe(III) in the layers, and different alkyl sulfonates in the interlayer, have been prepared and characterized by powder X-ray diffraction, FT-IR spectroscopy, differential thermal analysis and thermogravimetric analysis. Pure crystalline phases have been obtained in all cases. Upon heating, combustion of the organic chain takes place at lower temperature than the corresponding sodium salts.

Biodiesel synthesis using calcined layered double hydroxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schumaker, J. Link; Crofcheck, Czarena; TAckett, S. Adam

2008-01-01

The catalytic properties of calcined Li-Al, Mg-Al and Mg-Fe layered double hydroxides (LDHs) were examined in two transesterification reactions, namely, the reaction of glyceryl tributyrate with methanol, and the reaction of soybean oil with methanol. While the Li-Al catalysts showed high activity in these reactions at the reflux temperature of methanol, the Mg-Fe and Mg-Al catalysts exhibited much lower methyl ester yields. CO2 TPD measurements revealed the presence of sites of weak, medium and strong basicity on both Mg-Al and Li-Al catalysts, the latter showing higher concentrations of medium and strong base sites; by implication, these are the main sitesmore » active in transesterification catalyzed by calcined Li-Al LDHs. Maximum activity was observed for the Li-Al catalysts when a calcination temperature of 450-500 aC was applied, corresponding to decomposition of the layered double hydroxide to the mixed oxide without formation of crystalline lithium aluminate phases.« less

Elaidate-Intercalated hydrotalcite as a sorbent material for metalaxyl immobilitzation in soil

NASA Astrophysics Data System (ADS)

López-Cabeza, Rocío; Cornejo, Juan; Hermosín, María C.; Cox, Lucía; Celis, Rafael

2015-04-01

Layered double hydroxides (LDHs), also known as hydrotalcite-like compounds (HTs), comprise a special group of layered materials. Their structure consists of positively charged layers of mixed divalent (MII) and trivalent (MIII) metal hydroxide [MII1-xMIIIx(OH)2]x+, with the positive charge being balanced by inorganic hydrated anions (An-x/n·mH2O), which occupy the interlayer space. LDHs have anion exchange properties and, therefore, are good sorbents for anionic pollutants. In addition, the anionic exchange properties of LDHs allow the intercalation of organic anions in the interlayer space to render the LDH surface hydrophobic. This increases its affinity to hydrophobic organic compounds. Pesticides with chiral centers are an emerging class of organic pollutants and it has become clear that addressing the different efficacy, toxicity, and environmental behavior of chiral pesticide enantiomers is necessary to avoid the incorrect assumption that enantiomers have identical environmental behavior. Appropriate soil remediation strategies accounting for the enantioselective behavior of chiral pesticide enantiomers are also needed. In this work, we evaluated the performance of elaidate-modified hydrotalcite (HT-ELA) as a sorbent to remove the chiral fungicide metalaxyl from aqueous solution and as an amendment for metalaxyl immobilization in soil. Analysis of metalaxyl by chiral high-performance liquid chromatography allowed us to monitor the sorption and mobility of the two enantiomers of metalaxyl, S-(+)-metalaxyl and R-(-)-metalaxyl, independently. Batch sorption experiments showed that HT-ELA [Mg3Al(OH)8ELA] displayed an excellent performance as an sorbent of the two enantiomers of metalaxyl from aqueous solution and that its addition to a sandy loam agricultural soil at a rate of 1% greatly enhanced the sorption of metalaxyl enantiomers by the soil. Column leaching experiments demonstrated that amending the soil top layer (0-2.5 cm) with HT-ELA at a rate of 1% reduced the leaching of S- and R-metalaxyl. The R-enantiomer of metalaxyl leached less than the S-enantiomer due to its faster degradation in the soil. Our results illustrate the ability of elaidate-modified hydrotalcite to enhance the retention of the two enantiomers of the fungicide metalaxyl in the tested soil, which may be useful in the design of immobilization strategies, particularly of the more persistent S-metalaxyl enantiomer, which may represent increased risk of ground water contamination. Acknowledgments: MINECO Project AGL2011-23779, FACCE-JPI Project Designchar4food, JA Research Group AGR-264 and FEDER-FSE (OP 2007-2013).

A facile mechanochemical approach to synthesize Zn-Al layered double hydroxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jun, E-mail: forsjun@whut.edu.cn; He, Xiaoman; Chen, Min

2017-06-15

In this study, a mechanochemical route to synthesize Zn-Al layered double hydroxide (LDH) was introduced, in which Zn basic carbonate and Al hydroxide were first dry milled into an activated state and then agitated in water to obtain the final products. The as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry (TG) and Scanning electron microscopy (SEM). The products possessed a high crystallinity of Zn–Al LDH phase without any other impurities, proving a facile and effective preparation of Zn–Al LDH by using non-heating mechanochemical approach. - Highlights: • A non-heating mechanochemical route to synthesize Zn-Almore » LDH. • The products possessed high crystalline Zn-Al LDH phase. • No emission of other impurities or wastewater.« less

Cadmium-Aluminum Layered Double Hydroxide Microspheres for Photocatalytic CO2 Reduction.

PubMed

Saliba, Daniel; Ezzeddine, Alaa; Sougrat, Rachid; Khashab, Niveen M; Hmadeh, Mohamad; Al-Ghoul, Mazen

2016-04-21

We report the synthesis of cadmium-aluminum layered double hydroxide (CdAl LDH) using the reaction-diffusion framework. As the hydroxide anions diffuse into an agar gel matrix containing the mixture of aluminum and cadmium salts at a given ratio, they react to give the LDH. The LDH self-assembles inside the pores of the gel matrix into a unique spherical-porous shaped microstructure. The internal and external morphologies of the particles are studied by electron microscopy and tomography revealing interconnected channels and a high surface area. This material is shown to exhibit a promising performance in the photoreduction of carbon dioxide using solar light. Moreover, the palladium-decorated version shows a significant improvement in its reduction potential at room temperature. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

PubMed

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-05-09

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Layered double hydroxide films on nanoporous anodic aluminum oxide/aluminum wire: a new fiber for rapid analysis of Origanum vulgare essential oils.

PubMed

Piryaei, Marzieh

2018-01-01

Zn/Al layered double hydroxide (LDH) films were fabricated in situ with anodic aluminium oxide aluminium as both the substrate and the sole aluminium source by means of urea hydrolysis. Headspace solid phase microextraction using LDH fibre in combination with capillary GC-MS was utilised as a monitoring technique for the collection and detection of the volatile compounds of Origanum vulgare. Experimental parameters, including the sample weight, microwave power, extraction time and humidity effect, were examined and optimised.

Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maluangnont, Tosapol, E-mail: tosapol.ma@kmitl.ac.th; Catalytic Chemistry Research Unit, Faculty of Science, King Mongkut's Institute of Technology Ladkrabang, Bangkok 10520; Arsa, Pornanan

2016-06-15

While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O{sup 2−} sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} as an example. The low basicity (0.04 mmol CO{sub 2}/g) and low desorption temperature (50–300 °C) shown by CO{sub 2}− TPD suggests that O{sup 2−} sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO{sub 2}. The liquid-phase adsorptionmore » study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C{sub 16} acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O{sup 2−} sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast {sup 1}H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C{sub 31} ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at Ti{sup IV} sites was also illustrated. - Graphical abstract: Interlayer basic sites in lepidocrocite titanate, K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4}, lead to an intercalation of palmitic acid with a layer expansion. Display Omitted - Highlights: • K{sub 0.8}Zn{sub 0.4}Ti{sub 1.6}O{sub 4} intercalates palmitic acid, forming the occluded potassium salt. • The interlayer expansion is evidenced by PXRD patterns and TEM image. • Two types of basic sites are deduced from ultrafast {sup 1}H MAS NMR. • Lepidocrocite titanate catalyses ketonization of palmitic acid to palmitone and corresponding cracked products.« less

Inorganic Nanovehicle Targets Tumor in an Orthotopic Breast Cancer Model

NASA Astrophysics Data System (ADS)

Choi, Goeun; Kwon, Oh-Joon; Oh, Yeonji; Yun, Chae-Ok; Choy, Jin-Ho

2014-03-01

The clinical efficacy of conventional chemotherapeutic agent, methotrexate (MTX), can be limited by its very short plasma half-life, the drug resistance, and the high dosage required for cancer cell suppression. In this study, a new drug delivery system is proposed to overcome such limitations. To realize such a system, MTX was intercalated into layered double hydroxides (LDHs), inorganic drug delivery vehicle, through a co-precipitation route to produce a MTX-LDH nanohybrid with an average particle size of approximately 130 nm. Biodistribution studies in mice bearing orthotopic human breast tumors revealed that the tumor-to-liver ratio of MTX in the MTX-LDH-treated-group was 6-fold higher than that of MTX-treated-one after drug treatment for 2 hr. Moreover, MTX-LDH exhibited superior targeting effect resulting in high antitumor efficacy inducing a 74.3% reduction in tumor volume compared to MTX alone, and as a consequence, significant survival benefits. Annexin-V and propidium iodine dual staining and TUNEL analysis showed that MTX-LDH induced a greater degree of apoptosis than free MTX. Taken together, our data demonstrate that a new MTX-LDH nanohybrid exhibits a superior efficacy profile and improved distribution compared to MTX alone and has the potential to enhance therapeutic efficacy via inhibition of tumor proliferation and induction of apoptosis.

Inorganic nanovehicle targets tumor in an orthotopic breast cancer model.

PubMed

Choi, Goeun; Kwon, Oh-Joon; Oh, Yeonji; Yun, Chae-Ok; Choy, Jin-Ho

2014-03-21

The clinical efficacy of conventional chemotherapeutic agent, methotrexate (MTX), can be limited by its very short plasma half-life, the drug resistance, and the high dosage required for cancer cell suppression. In this study, a new drug delivery system is proposed to overcome such limitations. To realize such a system, MTX was intercalated into layered double hydroxides (LDHs), inorganic drug delivery vehicle, through a co-precipitation route to produce a MTX-LDH nanohybrid with an average particle size of approximately 130 nm. Biodistribution studies in mice bearing orthotopic human breast tumors revealed that the tumor-to-liver ratio of MTX in the MTX-LDH-treated-group was 6-fold higher than that of MTX-treated-one after drug treatment for 2 hr. Moreover, MTX-LDH exhibited superior targeting effect resulting in high antitumor efficacy inducing a 74.3% reduction in tumor volume compared to MTX alone, and as a consequence, significant survival benefits. Annexin-V and propidium iodine dual staining and TUNEL analysis showed that MTX-LDH induced a greater degree of apoptosis than free MTX. Taken together, our data demonstrate that a new MTX-LDH nanohybrid exhibits a superior efficacy profile and improved distribution compared to MTX alone and has the potential to enhance therapeutic efficacy via inhibition of tumor proliferation and induction of apoptosis.

One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

PubMed Central

Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, ZhiLi; Yang, Chunping; Hu, Xinjiang; Chen, Bo

2016-01-01

A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π–π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way. PMID:28000759

One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

NASA Astrophysics Data System (ADS)

Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, Zhili; Yang, Chunping; Hu, Xinjiang; Chen, Bo

2016-12-01

A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π-π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way.

Acute oral toxicity and biodistribution study of zinc-aluminium-levodopa nanocomposite

NASA Astrophysics Data System (ADS)

Kura, Aminu Umar; Saifullah, Bullo; Cheah, Pike-See; Hussein, Mohd Zobir; Azmi, Norazrina; Fakurazi, Sharida

2015-03-01

Layered double hydroxide (LDH) is an inorganic-organic nano-layered material that harbours drug between its two-layered sheets, forming a sandwich-like structure. It is attracting a great deal of attention as an alternative drug delivery (nanodelivery) system in the field of pharmacology due to their relative low toxic potential. The production of these nanodelivery systems, aimed at improving human health through decrease toxicity, targeted delivery of the active compound to areas of interest with sustained release ability. In this study, we administered zinc-aluminium-LDH-levodopa nanocomposite (ZAL) and zinc-aluminium nanocomposite (ZA) to Sprague Dawley rats to evaluate for acute oral toxicity following OECD guidelines. The oral administration of ZAL and ZA at a limit dose of 2,000 mg/kg produced neither mortality nor acute toxic signs throughout 14 days of the observation. The percentage of body weight gain of the animals showed no significant difference between control and treatment groups. Animal from the two treated groups gained weight continuously over the study period, which was shown to be significantly higher than the weight at the beginning of the study ( P < 0.05). Biochemical analysis of animal serum showed no significant difference between rats treated with ZAL, ZA and controls. There was no gross lesion or histopathological changes observed in vital organs of the rats. The results suggested that ZAL and ZA at 2,000 mg/kg body weight in rats do not induce acute toxicity in the animals. Elemental analysis of tissues of treated animals demonstrated the wider distribution of the nanocomposite including the brain. In summary, findings of acute toxicity tests in this study suggest that zinc-aluminium nanocomposite intercalated with and the un-intercalated were safe when administered orally in animal models for short periods of time. It also highlighted the potential distribution ability of Tween-80 coated nanocomposite after oral administration.

Nanostructured Layered Terbium Hydroxide Containing NASIDs: In Vitro Physicochemical and Biological Evaluations.

PubMed

Gu, Qing-Yang; Qiu, Xiao; Liu, Jing-Jing; Fu, Min; Chao, Jian-Ping; Ju, Rui-Jun; Li, Xue-Tao

2018-08-01

Diclofenac sodium (abrr. DS) and indomethacin (abrr. IMC) have been intercalated into the layered terbium hydroxide (LTbH) by anion exchange method. Chemical compositions, thermostability, morphology, luminescence property, release behaviors and cytotoxic effects have been investigated. The DS molecules may embed between layers with a bilayered arrangement and the IMC may correspond to a monolayered arrangement. The Tb3+ luminescence in DS-LTbH and IMC-LTbH composites were enhanced compared with LTbH precusor and the luminescence intensity increases with the deprotonation degree. Drug release was measured with HPLC, and LTbH showed sustained release behavior on both drugs. Further In Vitro evaluation were carried out on cancer cells. Cytotoxic effect of LTbH was observed with a sulforhodamine B colorimetric assay on a variety of cancer cell lines, which revealed that the LTbH showed little cytotoxic effect. Results indicate LTbH may offer a potential vehicle as an effective drug delivery system along with diagnostic integration.

Electrochemical Characterization of Vanadium Pentoxide (V 2O5) And Activated Carbon (AC) Electrodes in Multivalent Aluminum Nitrate (Al(NO3)3) Electrolyte for Battery-Type Hybrid Supercapacitor Applications

NASA Astrophysics Data System (ADS)

Solanki, Ketan Subhash

Hybrid supercapacitors (HSC) have been extensively investigated for enhanced charge storage capacity (Yoo, et al. 2014). Although Li-ion batteries are known for high energy density, but their limited power density has driven the research toward developing hybrid supercapacitors (Jayalakshmi and Balasubramanian 2008). They combine non-faradic properties of electric double layer capacitors (EDLC) and faradic properties of pseudocapacitors to provide high energy density without compromising high Power density (Yoo, et al. 2014) (Lukatskaya, Dunn and Gogotsi 2016). In HSC, one electrode will store energy by double layer mechanism whereas the other stores through redox intercalation or surface redox reactions (Lukatskaya, Dunn and Gogotsi 2016) (Karthikeyan, et al. 2010). In this study, we have examined the electrochemical characteristics of vanadium pentoxide (V2O5) and activated carbon (AC) in an aqueous multivalent aluminum nitrate (nonhydrate, Al(NO3)3) electrolyte for viable electrode applications in battery-type hybrid supercapacitors, also known as supercapattery. A Specific capacitance of 340 Fg -1 was obtained at a scanning rate of 10 mV/s. Although this configuration showed promising storage and cyclability capability but the voltage for intercalation of Al3+ ions occurred below zero voltage. Hence, right selection of electrodes for such configurations may help in obtaining intercalation and de-intercalation voltages above zero volt and thereby result in a viable practical application with better performance.

Modification of thermal and electronic properties of bilayer graphene by using slow Na+ ions

NASA Astrophysics Data System (ADS)

Ryu, Mintae; Lee, Paengro; Kim, Jingul; Park, Heemin; Chung, Jinwook

2016-12-01

Bilayer graphene (BLG) has an extensive list of industrial applications in graphene-based nanodevices such as energy storage devices, flexible displays, and thermoelectric devices. By doping slow Na+ ions on Li-intercalated BLG, we find significantly improved thermal and electronic properties of BLG by using angle-resolved photoemission and high-resolution core level spectroscopy (HRCLS) with synchrotron photons. Our HRCLS data reveal that the adsorbed Na+ ions on a BLG produced by Li-intercalation through single layer graphene (SLG) spontaneously intercalate below the BLG, and substitute Li atoms to form Na-Si bonds at the SiC interface while preserving the same phase of BLG. This is in sharp contrast with no intercalation of Na+ ions on SLG though neutral Na atoms intercalate. The Na+-induced BLG is found to be stable upon heating up to T = 400 °C, but returns to SLG when heated at T d = 500 °C. The evolution of the π-bands upon doping the Na+ ions followed by thermal annealing shows that the carrier concentration of the π-band may be artificially controlled without damaging the Dirac nature of the π-electrons. The doubled desorption temperature from that (T d = 250 °C) of the Na-intercalated SLG together with the electronic stability of the Na+-intercalated BLG may find more practical and effective applications in advancing graphene-based thermoelectric devices and anode materials for rechargeable batteries.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

PubMed

Martínez, José I; Laikhtman, Alex; Moon, Hoi Ri; Zak, Alla; Alonso, Julio A

2018-05-07

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS 2 multilayers and nanotubes. We find that H 2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H 2 on the surface of WS 2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H 2 between adjacent planar WS 2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H 2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H 2 monolayer adsorbed on top of the first WS 2 layer of a WS 2 multilayer system strongly facilitates the intercalation of H 2 between WS 2 layers underneath. This opens up an additional gate to intercalation processes.

Strategy for synthesizing quantum dot-layered double hydroxide nanocomposites and their enhanced photoluminescence and photostability.

PubMed

Cho, Seungho; Jung, Sungwook; Jeong, Sanghwa; Bang, Jiwon; Park, Joonhyuck; Park, Youngrong; Kim, Sungjee

2013-01-08

Layered double hydroxide-quantum dot (LDH-QD) composites are synthesized via a room temperature LDH formation reaction in the presence of QDs. InP/ZnS (core/shell) QD, a heavy metal free QD, is used as a model constituent. Interactions between QDs (with negative zeta potentials), decorated with dihydrolipoic acids, and inherently positively charged metal hydroxide layers of LDH during the LDH formations are induced to form the LDH-QD composites. The formation of the LDH-QD composites affords significantly enhanced photoluminescence quantum yields and thermal- and photostabilities compared to their QD counterparts. In addition, the fluorescence from the solid LDH-QD composite preserved the initial optical properties of the QD colloid solution without noticeable deteriorations such as red-shift or deep trap emission. Based on their advantageous optical properties, we also demonstrate the pseudo white light emitting diode, down-converted by the LDH-QD composites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petersen, Line Boisen; Lipton, Andrew S.; Zorin, Vadim

Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg{sub 1−x}Ga{sub x}(OH){sub 2}(NO{sub 3}){sub x}·yH{sub 2}O] was investigated using solid-state {sup 1}H and {sup 71}Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg{sub 3}-OH, Mg{sub 2}Ga-OH and intergallery water molecules were assigned and quantified using ({sup 1}H,{sup 71}Ga) HETCOR and {sup 1}H MAS NMR. A single {sup 71}Ga site originating from the unique Ga site in the MgGa LDH's was observed in {sup 71}Ga MAS and 3QMAS NMR spectra. Both {sup 1}H MAS NMR spectra recorded at 21.1 Tmore » (900 MHz) and elemental analysis show that the synthesized MgGa LDH's had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH){sub 4}]{sup −} complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of Ga-O-Ga connectivities or defects were detected for the MgGa LDH's. - Graphical abstract: Two types of hydroxides groups are observed in magnesium gallium layered double hydroxides revealing an ordering of Ga in the cation layer. - Highlights: • Ga is ordered in our magnesium gallium layered double hydroxides. • Ga depletion due to formation of soluble Ga complexes during synthesis. • No sign of Ga rich regions in magnesium gallium LDHs. • Solid state {sup 1}H and {sup 71}Ga give detailed insight into the structure.« less

New Lithium- and Diamine-Intercalated Superconductors Lix(CnH2n+4N2)yMoSe2 (n = 2,6)

NASA Astrophysics Data System (ADS)

Sato, Kazuki; Noji, Takashi; Hatakeda, Takehiro; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

2018-05-01

We have succeeded in synthesizing new intercalation superconductors Lix(C2H8N2)yMoSe2 and Lix(C6H16N2)yMoSe2 with Tc = 4.2 and 3.8-6.0 K, respectively, via the co-intercalation of lithium and ethylenediamine or hexamethylenediamine into semiconducting 2H-MoSe2. It has been found that the Tc values are related not to the interlayer spacing between MoSe2 layers so much but to the electronic density of states (EDOS) at the Fermi level. Moreover, only Li-intercalated LixMoSe2 with a small interlayer spacing has been found to be non-superconducting. Accordingly, it has been concluded that not only a sufficient amount of EDOS at the Fermi level due to the charge transfer from intercalated Li to MoSe2 layers but also the enhancement of the two-dimensionality of the crystal structure and/or electronic structure due to the expansion of the interlayer spacing between MoSe2 layers is necessary for the appearance of superconductivity in MoSe2-based intercalation superconductors. The pairing mechanism and the analogy to the superconductivity in the electric double-layer transistors of 2H-MoX2 (X = S, Se, Te) are discussed.

Ionic Liquids as Surfactants for Layered Double Hydroxide Fillers: Effect on the Final Properties of Poly(Butylene Adipate-Co-Terephthalate)

PubMed Central

Livi, Sébastien; Lins, Luanda Chaves; Peter, Jakub; Kredatusova, Jana; Pruvost, Sébastien

2017-01-01

In this work, phosphonium ionic liquids (ILs) based on tetra-alkylphosphonium cations combined with carboxylate, phosphate and phosphinate anions, were used for organic modification of layered double hydroxide (LDH). Two different amounts (2 and 5 wt %) of the organically modified LDHs were mixed with poly(butylene adipate-co-terephthalate) (PBAT) matrix by melt extrusion. All prepared PBAT/IL-modified-LDH composites exhibited increased mechanical properties (20–50% Young’s modulus increase), decreased water vapor permeability (30–50% permeability coefficient reduction), and slight decreased crystallinity (10–30%) compared to the neat PBAT. PMID:28956811

Anion-exchange membranes derived from quaternized polysulfone and exfoliated layered double hydroxide for fuel cells

NASA Astrophysics Data System (ADS)

Liu, Wan; Liang, Na; Peng, Pai; Qu, Rong; Chen, Dongzhi; Zhang, Hongwei

2017-02-01

Layered double hydroxides (LDH) are prepared by controlling urea assisted homogeneous precipitation conditions. Morphology and crystallinity of LDHs are confirmed by X-ray diffraction and scanning electron microscope. After LDHs are incorporated into quaternized polysulfone membranes, transmission electron microscope is used to observe the exfoliated morphology of LDH sheets in the membranes. The properties of the nanocomposite membranes, including water uptake, swelling ratio, mechanical property and ionic conductivity are investigated. The nanocomposite membrane containing 5% LDH sheets shows more balanced performances, exhibiting an ionic conductivity of 2.36×10-2 S cm-1 at 60 °C.

Efficient drug delivery using SiO2-layered double hydroxide nanocomposites.

PubMed

Li, Li; Gu, Zi; Gu, Wenyi; Liu, Jian; Xu, Zhi Ping

2016-05-15

MgAl-layered double hydroxide (MgAl-LDH) nanoparticles have great potentials in drug and siRNA delivery. In this work, we used a nanodot-coating strategy to prepare SiO2 dot-coated layered double hydroxide (SiO2@MgAl-LDH) nanocomposites with good dispersibility and controllable size for drug delivery. The optimal SiO2@MgAl-LDH nanocomposite was obtained by adjusting synthetic parameters including the mass ratio of MgAl-LDH to SiO2, the mixing temperature and time. The optimal SiO2@MgAl-LDH nanocomposite was shown to have SiO2 nanodots (10-15nm in diameter) evenly deposited on the surface of MgAl-LDHs (110nm in diameter) with the plate-like morphology and the average hydrodynamic diameter of 170nm. We further employed SiO2@MgAl-LDH nanocomposite as a nanocarrier to deliver methotrexate (MTX), a chemotherapy drug, to the human osteosarcoma cell (U2OS) and found that MTX delivered by SiO2@MgAl-LDH nanocomposite apparently inhibited the U2OS cell growth. Copyright © 2016 Elsevier Inc. All rights reserved.

Mena/VASP and αII-Spectrin complexes regulate cytoplasmic actin networks in cardiomyocytes and protect from conduction abnormalities and dilated cardiomyopathy

PubMed Central

2013-01-01

Background In the heart, cytoplasmic actin networks are thought to have important roles in mechanical support, myofibrillogenesis, and ion channel function. However, subcellular localization of cytoplasmic actin isoforms and proteins involved in the modulation of the cytoplasmic actin networks are elusive. Mena and VASP are important regulators of actin dynamics. Due to the lethal phenotype of mice with combined deficiency in Mena and VASP, however, distinct cardiac roles of the proteins remain speculative. In the present study, we analyzed the physiological functions of Mena and VASP in the heart and also investigated the role of the proteins in the organization of cytoplasmic actin networks. Results We generated a mouse model, which simultaneously lacks Mena and VASP in the heart. Mena/VASP double-deficiency induced dilated cardiomyopathy and conduction abnormalities. In wild-type mice, Mena and VASP specifically interacted with a distinct αII-Spectrin splice variant (SH3i), which is in cardiomyocytes exclusively localized at Z- and intercalated discs. At Z- and intercalated discs, Mena and β-actin localized to the edges of the sarcomeres, where the thin filaments are anchored. In Mena/VASP double-deficient mice, β-actin networks were disrupted and the integrity of Z- and intercalated discs was markedly impaired. Conclusions Together, our data suggest that Mena, VASP, and αII-Spectrin assemble cardiac multi-protein complexes, which regulate cytoplasmic actin networks. Conversely, Mena/VASP deficiency results in disrupted β-actin assembly, Z- and intercalated disc malformation, and induces dilated cardiomyopathy and conduction abnormalities. PMID:23937664

Mena/VASP and αII-Spectrin complexes regulate cytoplasmic actin networks in cardiomyocytes and protect from conduction abnormalities and dilated cardiomyopathy.

PubMed

Benz, Peter M; Merkel, Carla J; Offner, Kristin; Abeßer, Marco; Ullrich, Melanie; Fischer, Tobias; Bayer, Barbara; Wagner, Helga; Gambaryan, Stepan; Ursitti, Jeanine A; Adham, Ibrahim M; Linke, Wolfgang A; Feller, Stephan M; Fleming, Ingrid; Renné, Thomas; Frantz, Stefan; Unger, Andreas; Schuh, Kai

2013-08-12

In the heart, cytoplasmic actin networks are thought to have important roles in mechanical support, myofibrillogenesis, and ion channel function. However, subcellular localization of cytoplasmic actin isoforms and proteins involved in the modulation of the cytoplasmic actin networks are elusive. Mena and VASP are important regulators of actin dynamics. Due to the lethal phenotype of mice with combined deficiency in Mena and VASP, however, distinct cardiac roles of the proteins remain speculative. In the present study, we analyzed the physiological functions of Mena and VASP in the heart and also investigated the role of the proteins in the organization of cytoplasmic actin networks. We generated a mouse model, which simultaneously lacks Mena and VASP in the heart. Mena/VASP double-deficiency induced dilated cardiomyopathy and conduction abnormalities. In wild-type mice, Mena and VASP specifically interacted with a distinct αII-Spectrin splice variant (SH3i), which is in cardiomyocytes exclusively localized at Z- and intercalated discs. At Z- and intercalated discs, Mena and β-actin localized to the edges of the sarcomeres, where the thin filaments are anchored. In Mena/VASP double-deficient mice, β-actin networks were disrupted and the integrity of Z- and intercalated discs was markedly impaired. Together, our data suggest that Mena, VASP, and αII-Spectrin assemble cardiac multi-protein complexes, which regulate cytoplasmic actin networks. Conversely, Mena/VASP deficiency results in disrupted β-actin assembly, Z- and intercalated disc malformation, and induces dilated cardiomyopathy and conduction abnormalities.

Delaminating and restacking MgAl-layered double hydroxide monitored and characterized by a range of instrumental methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Somosi, Zoltán; Tóth, Ildikó Y.; Tombácz, Etelka; Sipos, Pál; Pálinkó, István

2017-07-01

The delamination-restacking properties of MgAl-layered double hydroxide (MgAl-LDH) were studied in various solvents. The LDH samples were successfully delaminated in polar amides (formamide, N-methylformamide, N-methylacetamide). Usually, delamination was finalized by ultrasonic treatment. As rehydrating solutions, numerous Na-salts with single-, double- and triple-charged anions were used. Reconstruction was accomplished with anions of one or two negative charges, but triple-charged ones generally disrupted the rebuilding process, likely, because their salts with the metals of the LDH are very stable, and the thin layers can more readily transform to salts than the ordered materials. Samples and delamination-restacking processes were characterized by X-ray diffractometry (XRD), infrared spectroscopy (IR), dynamic light scattering (DLS), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX).

Improving the Carprofen Solubility: Synthesis of the Zn2Al-LDH Hybrid Compound.

PubMed

Capsoni, Doretta; Quinzeni, Irene; Bruni, Giovanna; Friuli, Valeria; Maggi, Lauretta; Bini, Marcella

2018-01-01

The development of efficient strategies for drug delivery is considerably desired. Indeed, often several issues such as the drug solubility, the control of the drug release rate, the targeted delivery of drugs, the drug bioavailability, and the minimization of secondary effects still present great obstacles. Different methodologies have been proposed, but the use of nano-hybrids compounds that combine organic and inorganic substances seems particularly promising. An interesting inorganic host is the layered double hydroxide (LDH) with a sheets structure and formula [M 2+ 1-x M 3+ x (OH) 2 ](A n- ) x/n yH 2 O (M 2+  = Zn, Mg; M 3+  = Al; A n-  = nitrates, carbonates, chlorides). The possibility to exchange these counterions with drug molecules makes these systems ideal candidates for the drug delivery. In this article, we synthesize by co-precipitation method the hybrid compound Carprofen-Zn 2 Al-LDH. Carprofen, a poorly soluble anti-inflammatory drug, could also benefit of the association with a natural antacid such as LDH, to reduce the gastric irritation after its administration. Through X-ray diffraction and Fourier-transformed infrared spectroscopy (FT-IR), we could verify the effective drug intercalation into LDH. The dissolution tests clearly demonstrate a significant improvement of the drug release rate when carprofen is in the form of hybrid compound. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

A ruthenium dimer complex with a flexible linker slowly threads between DNA bases in two distinct steps.

PubMed

Bahira, Meriem; McCauley, Micah J; Almaqwashi, Ali A; Lincoln, Per; Westerlund, Fredrik; Rouzina, Ioulia; Williams, Mark C

2015-10-15

Several multi-component DNA intercalating small molecules have been designed around ruthenium-based intercalating monomers to optimize DNA binding properties for therapeutic use. Here we probe the DNA binding ligand [μ-C4(cpdppz)2(phen)4Ru2](4+), which consists of two Ru(phen)2dppz(2+) moieties joined by a flexible linker. To quantify ligand binding, double-stranded DNA is stretched with optical tweezers and exposed to ligand under constant applied force. In contrast to other bis-intercalators, we find that ligand association is described by a two-step process, which consists of fast bimolecular intercalation of the first dppz moiety followed by ∼10-fold slower intercalation of the second dppz moiety. The second step is rate-limited by the requirement for a DNA-ligand conformational change that allows the flexible linker to pass through the DNA duplex. Based on our measured force-dependent binding rates and ligand-induced DNA elongation measurements, we are able to map out the energy landscape and structural dynamics for both ligand binding steps. In addition, we find that at zero force the overall binding process involves fast association (∼10 s), slow dissociation (∼300 s), and very high affinity (Kd ∼10 nM). The methodology developed in this work will be useful for studying the mechanism of DNA binding by other multi-step intercalating ligands and proteins. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Facile synthesis of 3D MnNi-layered double hydroxides (LDH)/graphene composites from directly graphites for pseudocapacitor and their electrochemical analysis

NASA Astrophysics Data System (ADS)

Lee, Ilbok; Jeong, Gyoung Hwa; An, Soyeon; Kim, Sang-Wook; Yoon, Songhun

2018-01-01

Herein, MnNi-layered double hydroxides (LDH) were imbibed within the interlayers of graphene nanosheets. The anionic surfactant, sodium dodecyl sulfate played a role of graphite exfoliator adding interaction with metal cations. Using this process, layered MnNi-LDH-graphene nanocomposite was prepared without formation of graphene oxide. When applied into pseudocapacitor electrode, LDH-graphene with optimal ratio between Mn and Ni exhibited very stable cycle with 90% at 1400 cycles and high energy 47.29 Wh kg-1 at the power density of 7473 W kg-1, which was attributed to highly stable layered LDH structure within conductive graphene layers.

Preparation and regulating cell adhesion of anion-exchangeable layered double hydroxide micropatterned arrays.

PubMed

Yao, Feng; Hu, Hao; Xu, Sailong; Huo, Ruijie; Zhao, Zhiping; Zhang, Fazhi; Xu, Fujian

2015-02-25

We describe a reliable preparation of MgAl-layered double hydroxide (MgAl-LDH) micropatterned arrays on gold substrate by combining SO3(-)-terminated self-assembly monolayer and photolithography. The synthesis route is readily extended to prepare LDH arrays on the SO3(-)-terminated polymer-bonded glass substrate amenable for cell imaging. The anion-exchangeable MgAl-LDH micropattern can act both as bioadhesive region for selective cell adhesion and as nanocarrier for drug molecules to regulate cell behaviors. Quantitative analysis of cell adhesion shows that selective HepG2 cell adhesion and spreading are promoted by the micropatterned MgAl-LDH, and also suppressed by methotrexate drug released from the LDH interlayer galleries.

Water types and their relaxation behavior in partially rehydrated CaFe-mixed binary oxide obtained from CaFe-layered double hydroxide in the 155-298 K temperature range.

PubMed

Bugris, Valéria; Haspel, Henrik; Kukovecz, Ákos; Kónya, Zoltán; Sipiczki, Mónika; Sipos, Pál; Pálinkó, István

2013-10-29

Heat-treated CaFe-layered double hydroxide samples were equilibrated under conditions of various relative humidities (11%, 43% and 75%). Measurements by FT-IR and dielectric relaxation spectroscopies revealed that partial to full reconstruction of the layered structure took place. Water types taking part in the reconstruction process were identified via dielectric relaxation measurements either at 298 K or on the flash-cooled (to 155 K) samples. The dynamics of water molecules at the various positions was also studied by this method, allowing the flash-cooled samples to warm up to 298 K.

Mixed metal oxides for dye-sensitized solar cell using zinc titanium layered double hydroxide as precursor

NASA Astrophysics Data System (ADS)

Liu, Jianqiang; Qin, Yaowei; Zhang, Liangji; Xiao, Hongdi; Song, Jianye; Liu, Dehe; Leng, Mingzhe; Hou, Wanguo; Du, Na

2013-12-01

Mixed metal oxides (MMO) are always obtained from layered double hydroxide (LDH) by thermal decomposition. In the present work, a zinc titanium LDH with the zinc titanium molar ratio of 4.25 was prepared by urea method and ZnO-based mixed oxides were obtained by calcining at or over 500°C. The MMO was used as electrodes for dye sensitized solar cell (DSSC). The cells constructed by films of prepared composite materials using a N719 as dye were prepared. The efficiency values of these cells are 0.691%, 0.572% and 0.302% with MMO prepared at 500, 600 and 700°C, respectively.

Potassium-doped n-type bilayer graphene

NASA Astrophysics Data System (ADS)

Yamada, Takatoshi; Okigawa, Yuki; Hasegawa, Masataka

2018-01-01

Potassium-doped n-type bilayer graphene was obtained. Chemical vapor deposited bilayer and single layer graphene on copper (Cu) foils were used. After etching of Cu foils, graphene was dipped in potassium hydroxide aqueous solutions to dope potassium. Graphene on silicon oxide was characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopy. Both XPS and EDX spectra indicated potassium incorporation into the bilayer graphene via intercalation between the graphene sheets. The downward shift of the 2D peak position of bilayer graphene after the potassium hydroxide (KOH) treatment was confirmed in Raman spectra, indicating that the KOH-treated bilayer graphene was doped with electrons. Electrical properties were measured using Hall bar structures. The Dirac points of bilayer graphene were shifted from positive to negative by the KOH treatment, indicating that the KOH-treated bilayer graphene was n-type conduction. For single layer graphene after the KOH treatment, although electron doping was confirmed from Raman spectra, the peak of potassium in the X-ray photoelectron spectroscopy (XPS) spectrum was not detected. The Dirac points of single layer graphene with and without the KOH treatment showed positive.

Two-Dimensional Vanadium Carbide (MXene) as Positive Electrode for Sodium-Ion Capacitors.

PubMed

Dall'Agnese, Yohan; Taberna, Pierre-Louis; Gogotsi, Yury; Simon, Patrice

2015-06-18

Ion capacitors store energy through intercalation of cations into an electrode at a faster rate than in batteries and within a larger potential window. These devices reach a higher energy density compared to electrochemical double layer capacitor. Li-ion capacitors are already produced commercially, but the development of Na-ion capacitors is hindered by lack of materials that would allow fast intercalation of Na-ions. Here we investigated the electrochemical behavior of 2D vanadium carbide, V2C, from the MXene family. We investigated the mechanism of Na intercalation by XRD and achieved capacitance of ∼100 F/g at 0.2 mV/s. We assembled a full cell with hard carbon as negative electrode, a known anode material for Na ion batteries, and achieved capacity of 50 mAh/g with a maximum cell voltage of 3.5 V.

Lithium Titanate Confined in Carbon Nanopores for Asymmetric Supercapacitors.

PubMed

Zhao, Enbo; Qin, Chuanli; Jung, Hong-Ryun; Berdichevsky, Gene; Nese, Alper; Marder, Seth; Yushin, Gleb

2016-04-26

Porous carbons suffer from low specific capacitance, while intercalation-type active materials suffer from limited rate when used in asymmetric supercapacitors. We demonstrate that nanoconfinement of intercalation-type lithium titanate (Li4Ti5O12) nanoparticles in carbon nanopores yielded nanocomposite materials that offer both high ion storage density and rapid ion transport through open and interconnected pore channels. The use of titanate increased both the gravimetric and volumetric capacity of porous carbons by more than an order of magnitude. High electrical conductivity of carbon and the small size of titanate crystals allowed the composite electrodes to achieve characteristic charge and discharge times comparable to that of the electric double-layer capacitors. The proposed composite synthesis methodology is simple, scalable, and applicable for a broad range of active intercalation materials, while the produced composite powders are compatible with commercial electrode fabrication processes.

Insights into finding a mismatch through the structure of a mispaired DNA bound by a rhodium intercalator

PubMed Central

Pierre, Valérie C.; Kaiser, Jens T.; Barton, Jacqueline K.

2007-01-01

We report the 1.1-Å resolution crystal structure of a bulky rhodium complex bound to two different DNA sites, mismatched and matched in the oligonucleotide 5′-(dCGGAAATTCCCG)2-3′. At the AC mismatch site, the structure reveals ligand insertion from the minor groove with ejection of both mismatched bases and elucidates how destabilized mispairs in DNA may be recognized. This unique binding mode contrasts with major groove intercalation, observed at a matched site, where doubling of the base pair rise accommodates stacking of the intercalator. Mass spectral analysis reveals different photocleavage products associated with the two binding modes in the crystal, with only products characteristic of mismatch binding in solution. This structure, illustrating two clearly distinct binding modes for a molecule with DNA, provides a rationale for the interrogation and detection of mismatches. PMID:17194756

Ionic substitution of Mg2+ for Al3+ and Fe3+ with octahedral coordination in hydroxides facilitate precipitation of layered double hydroxides

NASA Astrophysics Data System (ADS)

Paikaray, Susanta; Essilfie-Dughan, Joseph; Hendry, M. Jim

2018-01-01

Precipitation of hydrotalcite-like layered double hydroxides (HT-LDHs) from CO32--SO42--rich acidic and alkaline aqueous media through ionic substitution of Mg2+ for Al3+ + Fe3+ and vice versa was investigated under ambient conditions. Diffractogram, spectroscopic, microprobe, microscopic, and synchrotron techniques were used to examine the mechanisms involved. The cations facilitated rapid precipitation of HT-LDH in alkaline conditions (pH ≥ 8.2) with SO42- and CO32- as the counter charge balancing interlayer anions, while initial formation of Fe3+- and Al3+-hydroxides in acidic conditions (pH ≥ 2.4) with subsequent transformation to MgAlFe-type HT-LDH (pH ≥ 8.2) occurred through substitution of Mg2+ for Al3+ and Fe3+. Substitution of Al3+ and Fe3+ in Mg2+-hydroxides did not yield HT-LDH, while the reverse, i.e., Mg2+ substitution in Al3+ and Fe3+-hydroxides, produced initial poorly ordered amorphous HT-LDH that gained better crystallinity and crystallite size upon neutralization. Linear combination fit analyses of XANES data suggest schwertmannite constituted the predominant Fe-phase until pH ∼3.7 followed by ferrihydrite and eventually HT-LDH after pH ≥ 10; basaluminite and epsomite constituted the predominant Al and Mg phases until pH ∼4.5, after which HT-LDH with minor Al(OH)3 and HT-LDH with brucite, respectively, predominated. The study highlights that Mg2+ substitution in Al- and Fe-precipitates is the governing mechanism for HT-LDH precipitation in oxic environments through neutralization of acidic cationic aqueous residues.

Ultrastructural and biochemical localization of N-RAP at the interface between myofibrils and intercalated disks in the mouse heart.

PubMed

Zhang, J Q; Elzey, B; Williams, G; Lu, S; Law, D J; Horowits, R

2001-12-11

N-RAP is a recently discovered muscle-specific protein found at cardiac intercalated disks. Double immunogold labeling of mouse cardiac muscle reveals that vinculin is located immediately adjacent to the fascia adherens region of the intercalated disk membrane, while N-RAP extends approximately 100 nm further toward the interior of the cell. We partially purified cardiac intercalated disks using low- and high-salt extractions followed by density gradient centrifugation. Immunoblots show that this preparation is highly enriched in desmin and junctional proteins, including N-RAP, talin, vinculin, beta1-integrin, N-cadherin, and connexin 43. Electron microscopy and immunolabeling demonstrate that N-RAP and vinculin are associated with the large fragments of intercalated disks that are present in this preparation, which also contains numerous membrane vesicles. Detergent treatment of the partially purified intercalated disks removed the membrane vesicles and extracted vinculin and beta1-integrin. Further separation on a sucrose gradient removed residual actin and myosin and yielded a fraction morphologically similar to fasciae adherentes that was highly enriched in N-RAP, N-cadherin, connexin 43, talin, desmin, and alpha-actinin. The finding that N-RAP copurifies with detergent-extracted intercalated disk fragments even though beta-integrin and vinculin have been completely removed suggests that N-RAP association with the adherens junction region is mediated by the cadherin system. Consistent with this hypothesis, we found that recombinant N-RAP fragments bind alpha-actinin in a gel overlay assay. In addition, immunofluorescence shows that N-RAP remains bound at the ends of isolated, detergent-treated cardiac myofibrils. These results demonstrate that N-RAP remains tightly bound to myofibrils and fasciae adherentes during biochemical purification and may be a key constituent in the mechanical link between these two structures.

Enhanced photocatalytic properties of the 3D flower-like Mg-Al layered double hydroxides decorated with Ag{sub 2}CO{sub 3} under visible light illumination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ao, Yanhui, E-mail: andyao@hhu.edu.cn; Wang, Dandan; Wang, Peifang

Highlights: • 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite was prepared. • The nanocomposites exhibited high photocatalytic activities on different organic pollutants. • The mechanism of the enhanced activity were investigated. - Abstract: A facile anion-exchange precipitation method was employed to synthesize 3D flower-like Ag{sub 2}CO{sub 3}/Mg-Al layered double hydroxide composite photocatalyst. Results showed that Ag{sub 2}CO{sub 3} nanoparticles dispersed uniformly on the petals of the flower-like Mg-Al LDH. The obtained nanocomposites exhibited high photocatalytic activities on different organic pollutants (cationic and anionic dyes, phenol) under visible light illumination. The high photocatalytic activity can be ascribed to themore » special structure which accomplishes the wide-distribution of Ag{sub 2}CO{sub 3} nanoparticles on the surfaces of the 3D flower-like nanocomposites. Therefore, it can provide much more active sites for the degradation of organic pollutant. Then the photocatalytic mechanism was also verified by reactive species trapping experiments in detail. The work would pave a facile way to prepare LDHs based hierarchical photocatalysts with high activity for the degradation of wide range organic pollutants under visible light irradiation.« less

Neocarzinostatin as a probe for DNA protection activity--molecular interaction with caffeine.

PubMed

Chin, Der-Hang; Li, Huang-Hsien; Kuo, Hsiu-Maan; Chao, Pei-Dawn Lee; Liu, Chia-Wen

2012-04-01

Neocarzinostatin (NCS), a potent mutagen and carcinogen, consists of an enediyne prodrug and a protein carrier. It has a unique double role in that it intercalates into DNA and imposes radical-mediated damage after thiol activation. Here we employed NCS as a probe to examine the DNA-protection capability of caffeine, one of common dietary phytochemicals with potential cancer-chemopreventive activity. NCS at the nanomolar concentration range could induce significant single- and double-strand lesions in DNA, but up to 75 ± 5% of such lesions were found to be efficiently inhibited by caffeine. The percentage of inhibition was caffeine-concentration dependent, but was not sensitive to the DNA-lesion types. The well-characterized activation reactions of NCS allowed us to explore the effect of caffeine on the enediyne-generated radicals. Postactivation analyses by chromatographic and mass spectroscopic methods identified a caffeine-quenched enediyne-radical adduct, but the yield was too small to fully account for the large inhibition effect on DNA lesions. The affinity between NCS chromophore and DNA was characterized by a fluorescence-based kinetic method. The drug-DNA intercalation was hampered by caffeine, and the caffeine-induced increases in DNA-drug dissociation constant was caffeine-concentration dependent, suggesting importance of binding affinity in the protection mechanism. Caffeine has been shown to be both an effective free radical scavenger and an intercalation inhibitor. Our results demonstrated that caffeine ingeniously protected DNA against the enediyne-induced damages mainly by inhibiting DNA intercalation beforehand. The direct scavenging of the DNA-bound NCS free radicals by caffeine played only a minor role. Copyright © 2011 Wiley Periodicals, Inc.

Binding mode and thermodynamic studies on the interaction of the anticancer drug dacarbazine and dacarbazine-Cu(II) complex with single and double stranded DNA.

PubMed

Temerk, Yassien; Ibrahim, Hossieny

2014-07-01

The binding mode and thermodynamic characteristics of the anticancer drug dacarbazine (Dac) with double and single stranded DNA were investigated in the absence and presence of Cu(II) using cyclic voltammetry, square wave voltammetry and fluorescence spectroscopy. The interaction of Dac and Dac-Cu(II) complex with dsDNA indicated their intercalation into the base stacking domain of dsDNA double helix and the strength of interaction is independent on the ionic strength. The interaction of Dac with dsDNA in the presence of Cu(II) leads to a much stronger intercalation. The interaction mode of Dac molecules with ssDNA is electrostatic attraction via negative phosphate on the exterior of the ssDNA with Dac. The binding constants, stoichiometric coefficients and thermodynamic parameters of Dac and Dac-Cu(II) complex with dsDNA and ssDNA were evaluated. Comparison of the mode interaction of Dac with dsDNA and ssDNA was discussed. The decrease of peak current of Dac was proportional to DNA concentration, which was applied for determination of dsDNA and ssDNA concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

Possible Mg intercalation mechanism at the Mo6 S8 cathode surface proposed by first-principles methods

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2015-03-01

In recent years, great attention has been paid to the development of divalent Mg-ion batteries, which can potentially double the energy density and volumetric capacity compared to monovalent Li-ion batteries. The prototype Mg-ion battery, comprising Mg(anode)/Mg(AlCl2BuEt)2.THF(electrolyte)/Mo6S8(cathode), was established in 2000 by Aurbach et al. Despite the remarkable success of this prototype system, we still lack a clear understanding of the fundamental Mg intercalation/deposition mechanism at the electrolyte/electrode interfaces that perhaps results in the observed sluggish Mg transport process. Our previous work has shown that Mg-ions are strongly coordinated in the bulk electrolyte by a combination of counterion, Cl-, and organic aprotic solvent, THF. In this work, we use first-principles methods to study Mg intercalation behavior at the Mo6S8 cathode surface with the presence of solvent molecules. It is found that the image charge, formed on this metallic cathode surface, can effectively weaken the solvent-surface interactions and facilitate Mg intercalation. A detailed Mg intercalation mechanism is proposed and the unique role of Mo6S8 as the cathode material is emphasized. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Preparation of pH-Responsive Hollow Capsules via Layer-by-Layer Assembly of Exfoliated Layered Double Hydroxide Nanosheets and Polyelectrolytes.

PubMed

Katagiri, Kiyofumi; Shishijima, Yoshinori; Koumoto, Kunihito; Inumaru, Kei

2018-01-01

pH-Responsive smart capsules were developed by the layer-by-layer assembly with a colloidtemplating technique. Polystyrene (PS) particles were employed as core templates. Acid-soluble inorganic nanosheets were prepared from Mg-Al layered double hydroxide (LDH) by an exfoliation technique. LDH nanosheets and anionic polyelectrolytes were alternatively deposited on PS core particles by the layer-by-layer assembly using electrostatic interaction. Hollow capsules were obtained by the removal of the PS core particles. The hollow capsules obtained thus were collapsed at acidic conditions by dissolution of LDH nanosheets in the hollow shells. The dissolution rate, i.e., the responsiveness of capsule, is tunable according to the strength of acids.

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

2018-02-01

In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

Tunable Properties of Exfoliated Polyvinylalcohol Nanocomposites by In Situ Coprecipitation of Layered Double Hydroxides

NASA Astrophysics Data System (ADS)

Liu, Jiajia; Yuen, Richard K. K.; Hu, Yuan

2017-10-01

Poly(vinyl alcohol) (PVA) nanocomposites were prepared by a “one step” method based on the coprecipitation of layered double hydroxide (LDH) nanosheets in the polymer aqueous solution. The morphology, fire resistance properties, mechanical and optical properties of the PVA/LDH nanocomposites were studied. The LDH nanosheets were homogeneously dispersed in the PVA matrix as indicated by X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) characterization. Meanwhile, the peak of heat release rate (pHRR) and total heat release (THR) were decreased by 58% and 28%, respectively. Storage modulus at 30 °C was increased, and the transmittance of more than 90% at the visible region was obtained upon addition of 5 wt% LDH.

Correlation between water absorption and mechanical properties of polyamide 6 filled with layered double hydroxides (LDH)

NASA Astrophysics Data System (ADS)

Botan, R.; Pinheiro, I. F.; Ferreira, F. V.; Lona, L. M. F.

2018-06-01

Polyamide 6 (PA6)/layered double hydroxide (LDH) nanocomposites were prepared by in situ polymerization with different amount (1, 2, 3 wt%) and type (Zn/Cr-L and Zn/Cr-P) of LDHs. The thermal and mechanical properties and water absorption capacity of PA6/LDH nanocomposites were investigated and have shown that the addition of LDHs increases the crystallinity of the polymer and improves their mechanical properties, while decreases the water absorption capacity due to a barrier effect of LDHs. A correlation between mechanical properties and water absorption capacity was observed and discussed. This study provides new strategies for tuning PA6-based nanocomposite properties, leading a progress in the development on the advanced polymer materials.

Transformation of zinc hydroxide chloride monohydrate to crystalline zinc oxide.

PubMed

Moezzi, Amir; Cortie, Michael; McDonagh, Andrew

2016-04-25

Thermal decomposition of layered zinc hydroxide double salts provides an interesting alternative synthesis for particles of zinc oxide. Here, we examine the sequence of changes occurring as zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2·H2O) is converted to crystalline ZnO by thermal decomposition. The specific surface area of the resultant ZnO measured by BET was 1.3 m(2) g(-1). A complicating and important factor in this process is that the thermal decomposition of zinc hydroxide chloride is also accompanied by the formation of volatile zinc-containing species under certain conditions. We show that this volatile compound is anhydrous ZnCl2 and its formation is moisture dependent. Therefore, control of atmospheric moisture is an important consideration that affects the overall efficiency of ZnO production by this process.

Preparation and Analysis of Libethenite: A Project for the First-Year Laboratory

ERIC Educational Resources Information Center

Ginion, Kelly E.; Yoder, Claude H.

2004-01-01

The preparation of libethenite, a double salt of copper(II) phosphate and copper(II) hydroxide presents the opportunity to discuss the prevalence of double salts in the environment, the relationship between solubility and stability in aqueous solution, the origin of the color of transition metal compounds and gravimetric analyses. Typical results…

Layered double hydroxide-enhanced luminescence in a Fenton-like system for selective sensing of cobalt in Hela cells

NASA Astrophysics Data System (ADS)

Yu, Mei; Yuan, Zhiqin; Lu, Chao

2017-09-01

This work presented a facile and eco-friendly method for the determination of cobalt ions (Co(II)) in living cells based on layered double hydroxides (Mg-Al CO3-LDHs) enhanced chemiluminescence (CL) emission of a Co(II)-hydrogen peroxide-sodium hydroxide system. The enhanced CL emission was attributed to the large specific surface area of Mg-Al CO3-LDHs, which facilitates the generation of an excited-stated intermediate. The proposed method displayed high selectivity toward Co(II) over other metal ions. Under the optimal conditions, the increased CL intensity showed a linear response versus Co(II) concentration in the range of 5.0-1000 nM with a detection limit of 3.7 nM (S/N = 3). The relative standard deviation for nine repeated measurements of 100 nM Co(II) was 3.2%. Furthermore, the proposed method was successfully applied to detect Co(II) in living cell samples, and the results were agreed with those obtained by the standard ICP-MS method.

Synthesis of layered double hydroxides containing Mg2+, Zn2+, Ca2+ and Al3+ layer cations by co-precipitation methods-A review

NASA Astrophysics Data System (ADS)

Theiss, Frederick L.; Ayoko, Godwin A.; Frost, Ray L.

2016-10-01

Co-precipitation is a common method for the preparation of layered double hydroxides (LDHs) and related materials. This review article is aimed at providing newcomers to the field with some examples of the types of co-precipitation reactions that have been reported previously and to briefly investigate some of the properties of the products of these reactions. Due to the sheer volume of literature on the subject, the authors have had to limit this article to the synthesis of Mg/Al, Zn/Al and Ca/Al LDHs by co-precipitation and directly related methods. LDHs have been synthesised from various reagents including metal salts, oxides and hydroxides. Co-precipitation is also useful for the direct synthesis of LDHs with a wide range of interlayer anions and various bases have been successfully employed to prepare LDHs. Examples of other synthesis techniques including the urea method, hydrothermal synthesis and various mechanochemical methods that are undoubtedly related to co-precipitation have also been included in this review. The effect of post synthesis hydrothermal has also been summarised.

Rate capability improvement of Co-Ni double hydroxides integrated in cathodically partially exfoliated graphite

NASA Astrophysics Data System (ADS)

Cai, Xiang; Song, Yu; Sun, Zhen; Guo, Di; Liu, Xiao-Xia

2017-10-01

In-situ growing of energy storage materials on graphene-based substrates/current collectors with low defect is a good way to boost electron transport and so enhance rate capability for the obtained electrode. Herein, high-quality graphene-like nanopetals are partially exfoliated from graphite foil (GF) through a facile and fast cathodic process. Three-dimensional porous structure is established for the afforded cathodically-exfoliated graphite foil (CEG), with many graphene-like nanopetals vertically anchoring on the graphite substrate. A hierarchical structure is constructed by the following electrochemical growth of Co-Ni double hydroxide nanopetals on the graphene atop CEG. The double hydroxide in the obtained electrode with the optimized Co2+/Ni2+ molar ratio, Co0.75Ni0.25(OH)2-CEG, displays much improved rate capability and so can deliver a high specific capacitance of 1460 F g-1 at an ultra-high current density of 100 A g-1. An asymmetric device is assembled by using Co0.75Ni0.25(OH)2-CEG as cathode, which demonstrates a high energy density of 31.6 Wh kg-1 at an ultra-high power density of 21.5 kW kg-1, showing the potential of the hierarchical composite electrode for high power application. The device also displays good stability, it can retain more than 90% of its capacitance after 10000 galvanostatic charge-discharge cycles.

Hierarchical Ni-Co layered double hydroxide nanosheets on functionalized 3D-RGO films for high energy density asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Jiang, Liyang; Sui, Yanwei; Qi, Jiqiu; Chang, Yuan; He, Yezeng; Meng, Qingkun; Wei, Fuxiang; Sun, Zhi; Jin, Yunxue

2017-12-01

In this paper, ultrathin reduced graphene oxide films on nickel foam were fabricated via a facile dip-coating method combined with thermal reduction. Hierarchical Ni-Co layered double hydroxide nanosheets with network structure were electrodeposited on the ultrathin reduced graphene oxide films in a simple three-electrode system. The thickness of Ni-Co layered double hydroxide nanosheets can be controlled through adjusting the deposition temperature. The as-prepared electrode exhibited excellent electrochemical performance with specific capacitance of 1454.2 F g-1 at a current density of 1 A g-1. An asymmetric supercapacitor device was designed with the as-prepared composites as positive electrode material and Nitrogen-doped reduced graphene oxide as negative electrode material. This device could be operated in a working voltage range of 0-1.8 V in 1 M KOH aqueous electrolyte, delivering a high energy density of 56.4 W h kg-1 at a power density of 882.5 W kg-1. One supercapacitor can power two LEDs with rated voltage of 1.8-2.0 V. After 10,000 consecutive charge-discharge tests at 10 A g-1, this asymmetric supercapacitor revealed an excellent cycle life with 98.3% specific capacitance retention. These excellent electrochemical performances make it become one of most promising candidates for high energy supercapacitor device.

Sandwich-like graphene/polypyrrole/layered double hydroxide nanowires for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Xuejin; Zhang, Yu; Xing, Wei; Li, Li; Xue, Qingzhong; Yan, Zifeng

2016-11-01

Electrode design in nanoscale is considered to be ultra-important to construct a superb capacitor. Herein, a sandwich-like composite was made by combining graphene/polypyrrole (GPPY) with nickel-aluminum layered double hydroxide nanowires (NiAl-NWs) via a facile hydrothermal method. This sandwich-like architecture is promising in energy storage applications due to three unique features: (1) the conductive GPPY substrate not only effectively prevents the layered double hydroxides species from aggregating, but also considerably facilitates the electron transmission; (2) the ultrathin NiAl-NWs ensure a maximum exposure of active Ni2+, which can improve the efficiency of rapid redox reactions even at high current densities; (3) the sufficient space between anisotropic NiAl-NWs can accommodate a large volume change of the nanowires to avoid their collapse or distortion during the reduplicative redox reactions. Keeping all these unique features in mind, when the as-prepared composite was applied to supercapacitors, it presented an enhanced capacitive performance in terms of high specific capacitance (845 F g-1), excellent rate performance (67% retained at 30 A g-1), remarkable cyclic stability (92% maintained after 5000 cycles) and large energy density (40.1 Wh·Kg-1). This accomplishment in the present work inspires an innovative strategy of nanoscale electrode design for high-rate performance supercapacitor electrodes containing pseuducapacitive metal oxide.

Structural, vibrational and morphological properties of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bezerra, Débora M.

2017-03-15

Layered double hydroxides are anionic clays with formula [M{sup II}{sub 1−x} M{sup III}{sub x}(OH){sub 2}]{sup q+}[A{sup n−}]{sub q/n}·mH{sub 2}O, finding possible uses as catalyst support, adsorbents and so on. In this paper, we address the phase formation of layered double hydroxides containing Ni{sup 2+}, Zn{sup 2+}, Al{sup 3+} and Zr{sup 4+} cations, namely, NiZn-Al, NiZn-AlZr and NiZn-Zr compositions obtained by the coprecipitation method. Such systems were characterized by X-ray diffraction, confirming the phase formation for NiZn-Al and NiZn-AlZr samples. Infrared and Raman spectroscopies elucidated the anion and water molecules occurrence in the interlayer. Nitrogen physisorption (BET method) determined the presencemore » of pores and specific surface area. The isotherm shapes were Type IV, according to the IUPAC, and represent a mesoporous structure. A morphological study was performed by means of scanning and transmission electron microscopies, and particle size values of 120, 131 and 235 nm for NiZn-Al, NiZn-AlZr and NiZn-Zr, respectively, were determined. Thermogravimetric analysis of the decomposition of the systems revealed that their complete disintegration occurred at ~ 450 °C and resulted in mixed oxides.« less

Layered-metal-hydroxide nanosheet arrays with controlled nanostructures to assist direct electronic communication at biointerfaces.

PubMed

An, Zhe; Lu, Shan; Zhao, Liwei; He, Jing

2011-10-18

In this work, ordered vertical arrays of layered double hydroxide (LDH) nanosheets have been developed to achieve electron transfer (eT) at biointerfaces in electrochemical devices. It is found that tailoring the gap size of LDH nanosheet arrays could significantly promote the eT rate. This research has successfully extended nanomaterials for efficient modifications of electrode surfaces from nanoparticles, nanowires, nanorods, and nanotubes to nanosheets. © 2011 American Chemical Society

The importance of proper crystal-chemical and geometrical reasoning demonstrated using layered single and double hydroxides

PubMed Central

Richardson, Ian G.

2013-01-01

Atomistic modelling techniques and Rietveld refinement of X-ray powder diffraction data are widely used but often result in crystal structures that are not realistic, presumably because the authors neglect to check the crystal-chemical plausibility of their structure. The purpose of this paper is to reinforce the importance and utility of proper crystal-chemical and geometrical reasoning in structural studies. It is achieved by using such reasoning to generate new yet fundamental information about layered double hydroxides (LDH), a large, much-studied family of compounds. LDH phases are derived from layered single hydroxides by the substitution of a fraction (x) of the divalent cations by trivalent. Equations are derived that enable calculation of x from the a parameter of the unit cell and vice versa, which can be expected to be of widespread utility as a sanity test for extant and future structure determinations and computer simulation studies. The phase at x = 0 is shown to be an α form of divalent metal hydroxide rather than the β polymorph. Crystal-chemically sensible model structures are provided for β-Zn(OH)2 and Ni- and Mg-based carbonate LDH phases that have any trivalent cation and any value of x, including x = 0 [i.e. for α-M(OH)2·mH2O phases]. PMID:23719702

Tens of micron-sized unilamellar nanosheets of Y/Eu layered rare-earth hydroxide: efficient exfoliation via fast anion exchange and their self-assembly into oriented oxide film with enhanced photoluminescence

NASA Astrophysics Data System (ADS)

Zhu, Qi; Li, Ji-Guang; Li, Xiaodong; Sun, Xudong; Qi, Yang; Zhu, Miaoyong; Sakka, Yoshio

2014-02-01

Layered rare-earth hydroxide (LRH) crystals of (Y0.95Eu0.05)2(OH)5NO3·nH2O with a lateral size of ˜ 300 μm and a thickness of ˜ 9 μm have been synthesized via a hydrothermal reaction of mixed nitrate solutions in the presence of mineralizer NH4NO3 at 200 °C for 24 h. LRH exhibits the ability to undergo intercalation and anion exchange with DS- (C12H25OSO3-) via hydrothermal treatment. Compared with traditional anion exchange at room temperature, hydrothermal processing not only shortens the anion exchange time from 720 to 24 h but also increases the basal spacing. The arrangements of DS- in the interlayer of LRH are significantly affected by the DS- concentration and reaction temperature, and the basal spacing of the LRH-DS sample in the crystal edge is assumed to be larger than that in the crystal center. A higher DS- concentration and reaction temperature both induce more intercalation of DS- anions into the interlayer gallery, thus yielding a larger basal spacing. Unilamellar nanosheets with a lateral size of ⩾60 μm and a thickness of ˜ 1.6 nm can be obtained by delaminating LRH-DS in formamide. The resultant unilamellar nanosheets are single crystalline. Transparent (Y0.95Eu0.05)2O3 phosphor films with a uniform [111] orientation and a layer thickness of ˜ 90 nm were constructed with the nanosheets as building blocks via spin-coating, followed by proper annealing. The oriented oxide film exhibits a strong red emission at 614 nm (the 5D0-7F2 transition of Eu3+), whose intensity is ˜ 2 times that of the powder form owing to the significant exposure of the (222) facets.

Gold Nanoparticles Supported on a Layered Double Hydroxide as Efficient Catalysts for the One-Pot Synthesis of Flavones.

PubMed

Yatabe, Takafumi; Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

2015-11-02

Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols). The present one-pot procedure consists of a sequence of several reactions, and Au/LDH can catalyze all these different types of reactions. The catalysis is shown to be truly heterogeneous, and Au/LDH can be readily recovered and reused. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel platform designed by Au core/inorganic shell structure conjugated onto MTX/LDH for chemo-photothermal therapy.

PubMed

Tian, De-Ying; Wang, Wei-Yuan; Li, Shu-Ping; Li, Xiao-Dong; Sha, Zhao-Lin

2016-05-30

A novel platform making up of methotrexate intercalated layered double hydroxide (MTX/LDH) hybrid doped with gold nanoparticles (NPs) may have great potential both in chemo-photothermal therapy and the simultaneous drug delivery. In this paper, a promising platform of Au@PDDA-MTX/LDH was developed for anti-tumor drug delivery and synergistic therapy. Firstly, Au NPs were coated using Layer-by-Layer (LbL) technology by alternate deposition of poly (diallyldimethylammonium chloride) (PDDA) and MTX molecules, and then the resulting core-shell structures (named as Au@PDDA-MTX) were directly conjugated onto the surface of MTX/LDH hybrid by electrostatic attraction to afford Au@PDDA-MTX/LDH NPs. Here MTX was used as both the agent for surface modification and the anti-tumor drug for chemotherapy. The platform of Au@PDDA-MTX/LDH NPs not only had a high drug-loading capacity, but also showed excellent colloidal stability and interesting pH-responsive release profile. In vitro drug release studies demonstrated that MTX released from Au@PDDA-MTX/LDH was relatively slow under normal physiological pH, but it was enhanced significantly at a weak acidic pH value. Furthermore, the combined treatment of cancer cells by using Au@PDDA-MTX/LDH for synergistic hyperthermia ablation and chemotherapy was demonstrated to exhibit higher therapeutic efficacy than either single treatment alone, underscoring the great potential of the platform for cancer therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Mg-Al and Zn-Al Layered Double Hydroxides Promote Dynamic Expression of Marker Genes in Osteogenic Differentiation by Modulating Mitogen-Activated Protein Kinases.

PubMed

Kang, Ha Ram; da Costa Fernandes, Célio Junior; da Silva, Rodrigo Augusto; Constantino, Vera Regina Leopoldo; Koh, Ivan Hong Jun; Zambuzzi, Willian F

2018-02-01

The effect of LDH samples comprised of chloride anions intercalated between positive layers of magnesium/aluminum (Mg-Al LDH) or zinc/aluminum (Zn-Al LDH) chemical composition on pre-osteoblast performance is investigated. Non-cytotoxic concentrations of both LDHs modulated pre-osteoblast adhesion by triggering cytoskeleton rearrangement dependent on recruiting of Cofilin, which is modulated by the inhibition of the Protein Phosphatase 2A (PP2A), culminating in osteoblast differentiation with a significant increase of osteogenic marker genes. The alkaline phosphatase (ALP) and bone sialoprotein (BSP) are significantly up-modulated by both LDHs; however, Mg-Al LDH nanomaterial promoted even more significance than both experimental controls, while the phosphorylations of mitogen-activated protein kinase (MAPKs)- extracellular signal-regulated kinases (ERK) and c-Jun N-terminal kinase (JNK) significantly increased. MAPK signaling is necessary to activate Runt-related transcription factor 2 (RUNX2) gene. Concomitantly, it is also investigated whether challenged osteoblasts are able to modulate osteoclastogenesis by investigating both osteoprotegerin (OPG) and Receptor activator of nuclear factor kappa-ligand (RANKL) in this model; a dynamic reprogramming of both these genes is found, suggesting LDHs in modulating osteoclastogenesis. These results suggest that LDHs interfere in bone remodeling, and they can be considered as nanomaterials in graft-based bone healing or drug-delivery materials for bone disorders. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic-scale recognition of surface structure and intercalation mechanism of Ti3C2X.

PubMed

Wang, Xuefeng; Shen, Xi; Gao, Yurui; Wang, Zhaoxiang; Yu, Richeng; Chen, Liquan

2015-02-25

MXenes represent a large family of functionalized two-dimensional (2D) transition-metal carbides and carbonitrides. However, most of the understanding on their unique structures and applications stops at the theoretical suggestion and lack of experimental support. Herein, the surface structure and intercalation chemistry of Ti3C2X are clarified at the atomic scale by aberration-corrected scanning transmission electron microscope (STEM) and density functional theory (DFT) calculations. The STEM studies show that the functional groups (e.g., OH(-), F(-), O(-)) and the intercalated sodium (Na) ions prefer to stay on the top sites of the centro-Ti atoms and the C atoms of the Ti3C2 monolayer, respectively. Double Na-atomic layers are found within the Ti3C2X interlayer upon extensive Na intercalation via two-phase transition and solid-solution reactions. In addition, aluminum (Al)-ion intercalation leads to horizontal sliding of the Ti3C2X monolayer. On the basis of these observations, the previous monolayer surface model of Ti3C2X is modified. DFT calculations using the new modeling help to understand more about their physical and chemical properties. These findings enrich the understanding of the MXenes and shed light on future material design and applications. Moreover, the Ti3C2X exhibits prominent rate performance and long-term cycling stability as an anode material for Na-ion batteries.

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition

NASA Astrophysics Data System (ADS)

Gill, Martin R.; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A.; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A.

2016-08-01

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)]2+ (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)]2+ before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition.

PubMed

Gill, Martin R; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A

2016-08-25

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)](2+) (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)](2+) before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

The hypocholesterolemic effect of an antacid containing aluminum hydroxide.

PubMed

Sperber, A D; Henkin, Y; Zuili, I; Bearman, J E; Shany, S

1991-12-01

To evaluate the efficacy, safety, and hypocholesterolemic effect of an aluminum hydroxide-containing antacid in hypercholesterolemic individuals. A prospective, randomized, double-masked, placebo-controlled phase of 2 months' duration, followed by an open-design treatment phase of 2 months' duration and a washout phase of 2 months' duration. Family practice clinics of two rural communities (kibbutzim) in Israel. Fifty-six men and women with hypercholesterolemia (type IIa or IIb). Fifty individuals completed the study. After 2 months of dietary modification (low-fat, low-cholesterol diet), the participants were randomized into two matched groups. Group 1 (28 participants) was treated for 2 months with a chewable antacid tablet containing simethicone, magnesium hydroxide, and 113 mg of aluminum hydroxide per tablet, at a dose of two tablets four times daily. Group 2 (22 participants) was given a similar number of placebo tablets for 2 months. During the following 2 months, both groups received the antacid at the above dose. Lipoprotein levels were evaluated at baseline and every 2 months thereafter for 6 months. Compared with pretreatment levels, Group 1 experienced a decrease in low-density lipoprotein cholesterol (LDL-C) of 9.8% after 2 months (p less than 0.001) and 18.5% after 4 months (p less than 0.001). Compared with Group 2, the decrease in LDL-C in Group 1 was 6.2% at the end of the 2-month double-masked, placebo phase. Although the high-density lipoprotein cholesterol (HDL-C) was also reduced in Group 1 at the end of 4 months of therapy (10.2%), the HDL-C/LDL-C ratio increased by 13% during the same interval (p less than 0.05). The treatment was well tolerated, with minimal side effects. An aluminum hydroxide-containing antacid reduces LDL-C in hypercholesterolemic individuals. Although HDL-C was also reduced to a lesser extent, the overall atherogenic index was improved. Further studies should be conducted to evaluate the long-term safety and efficacy of antacids containing aluminum hydroxide in hypercholesterolemic patients.

Surface Surgery of the Nickel-Rich Cathode Material LiNi0.815Co0.15Al0.035O2: Toward a Complete and Ordered Surface Layered Structure and Better Electrochemical Properties.

PubMed

Tang, Zhongfeng; Bao, Junjie; Du, Qingxia; Shao, Yu; Gao, Minghao; Zou, Bangkun; Chen, Chunhua

2016-12-21

A complete and ordered layered structure on the surface of LiNi 0.815 Co 0.15 Al 0.035 O 2 (NCA) has been achieved via a facile surface-oxidation method with Na 2 S 2 O 8 . The field-emission transmission electron microscopy images clearly show that preoxidation of the hydroxide precursor can eliminate the crystal defects and convert Ni(OH) 2 into layered β-NiOOH, which leads to a highly ordered crystalline NCA, with its (006) planes perpendicular to the surface in the sintering process. X-ray photoelectron spectroscopy and Raman shift results demonstrate that the contents of Ni 2+ and Co 2+ ions are reduced with preoxidization on the surface of the hydroxide precursor. The level of Li + /Ni 2+ disordering in the modified NCA determined by the peak intensity ratio I (003) /I (104) in X-ray diffraction patterns decreases. Thanks to the complete and ordered layered structure on the surface of secondary particles, lithium ions can easily intercalate/extract in the discharging-charging process, leading to greatly improved electrochemical properties.

X-ray-structure of a cytidylyl-3',5'-adenosine-proflavine complex: a self-paired parallel-chain double helical dimer with an intercalated acridine dye.

PubMed Central

Westhof, E; Sundaralingam, M

1980-01-01

The non-self-complementary dinucleoside monophosphate cytidylyl-3',5'-adenosine (CpA) forms a base-paired parallel-chain dimer with an intercalated proflavine. The dimer complex possesses a right-handed helical twist. The dimer helix has an irregular girth with a neutral adenine-adenine (A-A) pair, hydrogen-bonded through the N6 and N7 sites (C1'...C1' separation of 10.97 A), and a triply hydrogen-bonded protonated cytosine-cytosine (C-C) pair with a proton shared between the base N3 sites (Cl'...Cl' separation of 9.59 A). The torsion angles of the sugar-phosphate backbone are within their most preferred ranges and the sugar puckering sequence (5' leads to 3') is C3'-endo, C2'-endo. There is also a second proflavine molecule sandwiched between CpA dimers on the 21-axis. Both proflavines are necessarily disordered, being on dyad axis, and this suggests possible insights into the dynamics of intercalation of planar drugs. This structure shows that intercalation of planar drugs in nucleic acids may not be restricted to antiparallel complementary Watson-Crick pairing regions and provides additional mechanisms for acridine mutagenesis. PMID:6929524

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-08-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm-2 or 1734 F g-1 at 5 mA cm-2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application.

Hierarchical Co-based Porous Layered Double Hydroxide Arrays Derived via Alkali Etching for High-performance Supercapacitors

PubMed Central

Abushrenta, Nasser; Wu, Xiaochao; Wang, Junnan; Liu, Junfeng; Sun, Xiaoming

2015-01-01

Hierarchical nanoarchitecture and porous structure can both provide advantages for improving the electrochemical performance in energy storage electrodes. Here we report a novel strategy to synthesize new electrode materials, hierarchical Co-based porous layered double hydroxide (PLDH) arrays derived via alkali etching from Co(OH)2@CoAl LDH nanoarrays. This structure not only has the benefits of hierarchical nanoarrays including short ion diffusion path and good charge transport, but also possesses a large contact surface area owing to its porous structure which lead to a high specific capacitance (23.75 F cm−2 or 1734 F g−1 at 5 mA cm−2) and excellent cycling performance (over 85% after 5000 cycles). The enhanced electrode material is a promising candidate for supercapacitors in future application. PMID:26278334

Insitu grown superhydrophobic Zn-Al layered double hydroxides films on magnesium alloy to improve corrosion properties

NASA Astrophysics Data System (ADS)

Zhou, Meng; Pang, Xiaolu; Wei, Liang; Gao, Kewei

2015-05-01

A hierarchical superhydrophobic zinc-aluminum layered double hydroxides (Zn-Al LDHs) film has been fabricated on a magnesium alloy substrate via a facile hydrothermal crystallization method following chemical modification. The characteristics of the films were investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM), and energy dispersive spectroscopy (EDS). XRD patterns and SEM images showed that the micro/nanoscale hierarchical LDHs film surfaces composed of ZnO nanorods and Zn-Al LDHs nanowalls structures. The static contact angle (CA) for the prepared surfaces was observed at around 165.6°. The corrosion resistance of the superhydrophobic films was estimated by electrochemical impedance spectroscopy (EIS) and potentiondynamic polarization measurement. EIS and polarization measurements revealed that the superhydrophobic Zn-Al LDHs coated magnesium alloy had better corrosion resistance in neutral 3.5 wt.% NaCl solution.

Mechanochemical approach for synthesis of layered double hydroxides

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqing; Li, Shuping

2013-06-01

In this paper, a mechanochemical approach is used to prepare layered double hydroxides (LDHs). This approach involves manually grinding the precursor, nitrates and then the hydrothermal treatment. The study indicates that grinding leads to the incomplete formation of LDHs phase, LDHs-M. The reaction degree of precursor salts to LDHs after grinding depends on the melting points of the precursors. As expected, hydrothermal treatment is beneficial for the good crystallization and regularity of LDHs. Especially, the effect of hydrothermal treatment has been emphatically explored. The hydration of LDHs-M, increment of zeta potentials and the complete exchange of NO3- by CO32- anions occur successively or in parallel during the hydrothermal treatment. It can be found that combination of grinding and hydrothermal treatment gives rise to the formation of uniform and monodispersed particles of LDHs.

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Microwave-assisted synthesis of metal oxide/hydroxide composite electrodes for high power supercapacitors - A review

NASA Astrophysics Data System (ADS)

Faraji, Soheila; Ani, Farid Nasir

2014-10-01

Electrochemical capacitors (ECs), also known as pseudocapacitors or supercapacitors (SCs), is receiving great attention for its potential applications in electric and hybrid electric vehicles because of their ability to store energy, alongside with the advantage of delivering the stored energy much more rapidly than batteries, namely power density. To become primary devices for power supply, supercapacitors must be developed further to improve their ability to deliver high energy and power simultaneously. In this concern, a lot of effort is devoted to the investigation of pseudocapacitive transition-metal-based oxides/hydroxides such as ruthenium oxide, manganese oxide, cobalt oxide, nickel oxide, cobalt hydroxide, nickel hydroxide, and mixed metal oxides/hydroxides such as nickel cobaltite and nickel-cobalt oxy-hydroxides. This is mainly due to the fact that they can produce much higher specific capacitances than typical carbon-based electric double-layer capacitors and electronically conducting polymers. This review presents supercapacitor performance data of metal oxide thin film electrodes by microwave-assisted as an inexpensive, quick and versatile technique. Supercapacitors have established the specific capacitance (Cs) principles, therefore, it is likely that metal oxide films will continue to play a major role in supercapacitor technology and are expected to considerably increase the capabilities of these devices in near future.

Electrochemical immunosensor with NiAl-layered double hydroxide/graphene nanocomposites and hollow gold nanospheres double-assisted signal amplification.

PubMed

Qiao, Lu; Guo, Yemin; Sun, Xia; Jiao, Yancui; Wang, Xiangyou

2015-08-01

A sensitive electrochemical immunosensor based on NiAl-layered double hydroxide/graphene nanocomposites (NiAl-LDH/G) and hollow gold nanospheres (HGNs) was proposed for chlorpyrifos detection. The NiAl-LDH/G was prepared using a conventional coprecipitation process and reduction of the supporting graphene oxide. Subsequently, the nanocomposites were dispersed with chitosan (CS). The NiAl-LDH/G possessed good electrochemical behavior and high binding affinity to the electrode. The high surface areas of HGNs and the vast aminos and hydroxyls of CS provided a platform for the covalently crosslinking of antibody. Under optimal conditions, the immunosensor exhibited a wide linear range from 5 to 150 μg/mL and from 150 to 2 μg/mL, with a detection limit of 0.052 ng/mL. The detection results showed good agreement with standard gas chromatography method. The constructed immunosensor exhibited good reproducibility, high specificity, acceptable stability and regeneration performance, which provided a new promising tool for chlorpyrifos detection in real samples.

Energy storage mechanism in aqueous fiber-shaped Li-ion capacitors based on aligned hydrogenated-Li4Ti5O12 nanowires.

PubMed

Zhao, Hao; Ma, Xiangwen; Bai, Jinglong; Yang, Zhenyu; Sun, Gengzhi; Zhang, Zhenxing; Pan, Xiaojun; Lan, Wei; Zhou, Jin Yuan; Xie, Erqing

2017-06-22

It is reported that Li ions can contribute a lot to the capacitance of aqueous Li-ion capacitors (LICs), which might be due to the intercalation/de-intercalation processes of Li + ions that also occur at the anodes. However the energy storage mechanism in the aqueous LIC system still requires further proof. In this work, a type of aqueous fiber-shaped LIC has been designed and developed using hydrogenated Li 4 Ti 5 O 12 (H-LTO) anodes, active carbon (AC) cathodes, and LiCl/PVA gel electrolytes with a double-helical structure. The obtained single LTO wire electrode exhibits a high specific capacitance in volume (34.1 F cm -3 ) and superior cycling stabilities (∼100% over 100 000 cycles), both of which are due to the formed amorphous layers at the surface of the electrodes. Moreover, it is found via sweep voltammetry analysis that most of the energy stored in an aqueous fiber-shaped capacitor electrode is attributed to the Li ions' intercalation, whose content exceeds 85% at a low scan rate and gradually decreases with increasing scan rate; while the energy stored by the double electric layers remains almost unchanged with different scan rates. Furthermore, the well-matched wearable fiber-shaped LICs show high capacitive behaviors (18.44 μW h cm -2 ) and superior static/dynamic cycling stabilities. This research would provide some insight into the charge storage mechanism in electrodes in the aqueous system, and give more suggestions to develop high-energy-density fiber-shaped energy storage devices.

NIR‐Triggered Crystal Phase Transformation of NiTi‐Layered Double Hydroxides Films for Localized Chemothermal Tumor Therapy

PubMed Central

Wang, Donghui; Ge, Naijian; Yang, Tingting; Peng, Feng; Qiao, Yuqin; Li, Qianwen

2018-01-01

Abstract Construction of localized drug‐eluting systems with synergistic chemothermal tumor‐killing abilities is promising for biomedical implants directly contacting with tumor tissues. In this study, an intelligent and biocompatible drug‐loading platform, based on a gold nanorods‐modified butyrate‐inserted NiTi‐layered double hydroxides film (Au@LDH/B), is prepared on the surface of nitinol alloy. The prepared films function as drug‐loading “sponges,” which pump butyrate out under near‐infrared (NIR) irradiation and resorb drugs in water when the NIR laser is shut off. The stimuli‐responsive release of butyrate is verified to be related with the NIR‐triggered crystal phase transformation of Au@LDH/B. In vitro and in vivo studies reveal that the prepared films possess excellent biosafety and high efficiency in synergistic thermochemo tumor therapy, showing a promising application in the construction of localized stimuli‐responsive drug‐delivery systems. PMID:29721424

Confinement of carbon dots localizing to the ultrathin layered double hydroxides toward simultaneous triple-mode bioimaging and photothermal therapy.

PubMed

Weng, Yangziwan; Guan, Shanyue; Lu, Heng; Meng, Xiangmin; Kaassis, Abdessamad Y; Ren, Xiaoxue; Qu, Xiaozhong; Sun, Chenghua; Xie, Zheng; Zhou, Shuyun

2018-07-01

It is a great challenge to develop multifunctional nanocarriers for cancer diagnosis and therapy. Herein, versatile CDs/ICG-uLDHs nanovehicles for triple-modal fluorescence/photoacoustic/two-photon bioimaging and effective photothermal therapy were prepared via a facile self-assembly of red emission carbon dots (CDs), indocyanine green (ICG) with the ultrathin layered double hydroxides (uLDHs). Due to the J-aggregates of ICG constructed in the self-assembly process, CDs/ICG-uLDHs was able to stabilize the photothermal agent ICG and enhanced its photothermal efficiency. Furthermore, the unique confinement effect of uLDHs has extended the fluorescence lifetime of CDs in favor of bioimaging. Considering the excellent in vitro and in vivo phototherapeutics and multimodal imaging effects, this work provides a promising platform for the construction of multifunctional theranostic nanocarrier system for the cancer treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Wearable high-performance supercapacitors based on Ni-coated cotton textile with low-crystalline Ni-Al layered double hydroxide nanoparticles.

PubMed

Lu, Haicui; Chen, Jizhang; Tian, Qinghua

2018-03-01

Wearable electronics are developing rapidly in recent years. In this work, we develop a cost-effective, facile, and scalable approach to transform insulating cotton textile to highly conductive Ni-coated cotton textile (NCT). In order to verify the feasibility of NCT as a flexible current collector for wearable supercapacitors, we electrodeposit low-crystalline Ni-Al layered double hydroxide (LDH) nanoparticles onto the NCT. The obtained NCT@NiAl-LDH shows high specific capacitance (935.2 mF cm -2 ), superior rate capability, and good cyclability. Besides, the asymmetric supercapacitor (ASC) assembled from NCT@NiAl-LDH exhibits high specific energy of 58.8 Wh kg -1 (134 μWh cm -2 ) when the specific power is 539 W kg -1 (1228 μW cm -2 ). The results demonstrate great potential of our methodology. Copyright © 2017 Elsevier Inc. All rights reserved.

In situ fabrication of nickel aluminum-layered double hydroxide nanosheets/hollow carbon nanofibers composite as a novel electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

He, Fang; Hu, Zhibiao; Liu, Kaiyu; Zhang, Shuirong; Liu, Hongtao; Sang, Shangbin

2014-12-01

This paper introduces a new design route to fabricate nickel aluminum-layered double hydroxide (NiAl-LDH) nanosheets/hollow carbon nanofibers (CNFs) composite through an in situ growth method. The NiAl-LDH thin layers which grow on hollow carbon nanofibers have an average thickness of 13.6 nm. The galvanostatic charge-discharge test of the NiAl-LDH/CNFs composite yields an impressive specific capacitance of 1613 F g-1 at 1 A g-1 in 6 M KOH solution, the composite shows a remarkable specific capacitance of 1110 F g-1 even at a high current density of 10 A g-1. Furthermore, the composite remains a specific capacitance of 1406 F g-1 after 1000 cycles at 2 A g-1, indicating the composite has excellent high-current capacitive behavior and good cycle stability in compared to pristine NiAl-LDH.

Pulse electrodeposition of CoFe thin films covered with layered double hydroxides as a fast route to prepare enhanced catalysts for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Sakita, Alan M. P.; Noce, Rodrigo Della; Vallés, Elisa; Benedetti, Assis V.

2018-03-01

A novel, ultra-fast, and one-step method for obtaining an effective catalyst for oxygen evolution reaction is proposed. The procedure consists in direct electrodeposition, in a free-nitrate bath, of CoFe alloy films covered with layered double hydroxides (LDH), by potentiostatic mode, in continuous or pulsed regime. The catalyst is directly formed on glassy carbon substrates. The best-prepared catalyst material reveals a mixed morphology with granular and dendritic CoFe alloy covered with a sponge of CoFe-LDH containing a Cl interlayer. An overpotential of η10 mA = 286 mV, with a Tafel slope of 48 mV dec-1, is obtained for the OER which displays the enhanced properties of the catalyst. These improved results demonstrate the competitiveness and efficacy of our proposal for the production of OER catalysts.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System.

PubMed

Lavrynenko, O M; Pavlenko, O Yu; Shchukin, Yu S

2016-12-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Fabrication of nanocomposites by collagen templated synthesis of layered double hydroxides assisted by an acrylic silane coupling agent

NASA Astrophysics Data System (ADS)

Sun, Yanqing; Zhou, Yuming; Wang, Zhiqiang; Ye, Xiaoyun

2009-02-01

The purpose of this study was to control the fabrication of nanocomposites at the nanoscale interface by collagen templated synthesis of Zn-Al layered double hydroxides (LDHs) assisted by γ-methacryloxypropyl trimethoxy silane (KH570) with further treatment of graft polymerization. The results show that collagen directs the growth of LDHs into curved nanorods by length of 300 nm in perfect consistency with collagen chain in both the size and flexility under the essential hydrophobic environment on the solid surface provided by KH570. The nanorods are aggregated into thin curved platelets due to strong interaction between collagen molecules themselves and strong interaction between collagen and LDH sheets. By further treatment of graft polymerization, the adjacent curved platelets encircle into numerous hollows via chemical linkage, achieving polyporous nanocomposites. Nanohybrid materials with this structure are especially interesting for applications as biosensors or supported catalysis.

Improvement of pharmacokinetic and antitumor activity of layered double hydroxide nanoparticles by coating with PEGylated phospholipid membrane

PubMed Central

Yan, Mina; Zhang, Zhaoguo; Cui, Shengmiao; Lei, Ming; Zeng, Ke; Liao, Yunhui; Chu, Weijing; Deng, Yihui; Zhao, Chunshun

2014-01-01

Layered double hydroxide (LDH) has attracted considerable attention as a drug carrier. However, because of its poor in vivo behavior, polyethylene glycolylated (PEGylated) phospholipid must be used as a coformer to produce self-assembled core–shell nanoparticles. In the present study, we prepared a PEGylated phospholipid-coated LDH (PLDH) (PEG-PLDH) delivery system. The PEG-PLDH nanoparticles had an average size of 133.2 nm. Their core–shell structure was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. In vitro liposome-cell-association and cytotoxicity experiments demonstrated its ability to be internalized by cells. In vivo studies showed that PEGylated phospholipid membranes greatly reduced the blood clearance rate of LDH nanoparticles. PEG-PLDH nanoparticles demonstrated a good control of tumor growth and increased the survival rate of mice. These results suggest that PEG-PLDH nanoparticles can be a useful drug delivery system for cancer therapy. PMID:25364245

Computational NMR, IR/RAMAN calculations in sodium pravastatin: Investigation of the Self-Assembled Nanostructure of Pravastatin-LDH (Layered Double Hydroxides) Systems

NASA Astrophysics Data System (ADS)

Petersen, Philippe; Cunha, Vanessa; Gonçalves, Marcos; Petrilli, Helena; Constantino, Vera; Instituto de Física, Departamento de Física de Materiais e Mecânica Team; Instituto de Química, Departamento de Química Fundamental Team

2013-03-01

Layered double hydroxides (LDH) can be used as nanocontainers for immobilization of Pravastatin, in order to obtain suitable drug carriers. The material's structure and spectroscopic properties were analyzed by NMR, IR/RAMAN and supported by theoretical calculations. Density Functional Theory (DFT) calculations were performed using the Gaussian03 package. The geometry optimizations were performed considering the single crystal X-ray diffraction data of tert-octylamonium salt of Pravastatin. Tetramethylsilane (TMS), obtained with the same basis set, was used as reference for calculating the chemical shift of 13C. A scaling factor was used to compare theoretical and experimental harmonic vibrational frequencies. Through the NMR and IR/RAMAN spectra, we were able to make precise assignments of the NMR and IR/RAMAN of Sodium Pravastatin. We acknowledge support from CAPES, INEO and CNPQ.

Characteristic of the Nanoparticles Formed on the Carbon Steel Surface Contacting with 3d-Metal Water Salt Solutions in the Open-Air System

NASA Astrophysics Data System (ADS)

Lavrynenko, O. M.; Pavlenko, O. Yu; Shchukin, Yu S.

2016-02-01

The contact of a steel electrode with water dispersion medium in an open-air system leads to the development of various polymorphic iron oxides and oxyhydroxides on the steel surface. Whereas the usage of distilled water causes the obtaining of Fe(II)-Fe(III) layered double hydroxides (green rust) as a primary mineral phase, but in the presence of inorganic 3d-metal water salt solutions, mixed layered double hydroxides (LDHs) together with non-stoichiometric spinel ferrite nanoparticles are formed on the steel surface. Mixed LDHs keep stability against further oxidation and complicate the obtaining of spinel ferrite nanoparticles. Thermal treatment of mixed LDHs among other mineral phases formed via the rotation-corrosion dispergation process at certain temperatures permits to obtain homogenous nanoparticles of spinel ferrites as well as maghemite or hematite doped by 3d-metal cations.

Stabilization of Co{sup 2+} in layered double hydroxides (LDHs) by microwave-assisted ageing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herrero, M.; Benito, P.; Labajos, F.M.

2007-03-15

Co-containing layered double hydroxides at different pH have been prepared, and aged following different routes. The solids prepared have been characterized by element chemical analysis, powder X-ray diffraction, thermogravimetric and differential thermal analyses (both in nitrogen and in oxygen), FT-IR and Vis-UV spectroscopies, temperature-programmed reduction and surface area assessment by nitrogen adsorption at -196 deg. C. The best conditions found to preserve the cobalt species in the divalent oxidation state are preparing the samples at controlled pH, and then submit them to ageing under microwave irradiation. - Graphical abstract: The use of microwave-hydrothermal treatment, controlling both temperature and ageing time,more » permits to synthesize well-crystallized nanomaterials with controlled surface properties. An enhancement in the crystallinity degree and an increase in the particle size are observed when the irradiation time is prolonged.« less

A polarized view on DNA under tension

NASA Astrophysics Data System (ADS)

van Mameren, Joost; Vermeulen, Karen; Wuite, Gijs J. L.; Peterman, Erwin J. G.

2018-03-01

In the past decades, sensitive fluorescence microscopy techniques have contributed significantly to our understanding of the dynamics of DNA. The specific labeling of DNA using intercalating dyes has allowed for quantitative measurement of the thermal fluctuations the polymers undergo. On the other hand, recent advances in single-molecule manipulation techniques have unraveled the mechanical and elastic properties of this intricate polymer. Here, we have combined these two approaches to study the conformational dynamics of DNA under a wide range of tensions. Using polarized fluorescence microscopy in conjunction with optical-tweezers-based manipulation of YOYO-intercalated DNA, we controllably align the YOYO dyes using DNA tension, enabling us to disentangle the rapid dynamics of the dyes from that of the DNA itself. With unprecedented control of the DNA alignment, we resolve an inconsistency in reports about the tilted orientation of intercalated dyes. We find that intercalated dyes are on average oriented perpendicular to the long axis of the DNA, yet undergo fast dynamics on the time scale of absorption and fluorescence emission. In the overstretching transition of double-stranded DNA, we do not observe changes in orientation or orientational dynamics of the dyes. Only beyond the overstretching transition, a considerable depolarization is observed, presumably caused by an average tilting of the DNA base pairs. Our combined approach thus contributes to the elucidation of unique features of the molecular dynamics of DNA.

Chemically functionalized two-dimensional titanium carbide MXene by in situ grafting-intercalating with diazonium ions to enhance supercapacitive performance

NASA Astrophysics Data System (ADS)

Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Jiang, Quanguo

2018-04-01

Two-dimensional Ti3C2 MXene nanosheets were functionalized with phenylsulfonic groups derived from in situ generated diazonium ions by the corresponding amine. During the functionalization process, the aryl groups were attached onto the MXene surfaces in the form of strong MXene-aryl (Tisbnd Osbnd C) linkages. Simultaneously, the intercalation of diazonium ions enabled Ti3C2 multi-layers to be delaminated into separate few-layer nanosheets via weak sonication with low energy. As a result of chemical functionalization for MXene Ti3C2, the dispersibility was greatly improved and the specific surface area increased significantly. The grafted functional groups are still stable up to at least 200 °C upon thermogravimetric analysis measurements. With diazonium ions intercalating and electroactive groups grafting between-in MXene layers, the chemically functionalized Ti3C2 electrodes exhibited an enhanced supercapacitive performance, which acquired a specific capacitance more than double that of pristine Ti3C2 samples and excellent cycling stability (91% capacity retention after 10,000 cycles at 3 A g-1). This feasible modification scheme can be also extended to functionalize other types of MXenes materials with this or other aryl diazonium ions as surface modifiers and intercalants, thus offering scope for full potential applications of the new 2D materials.

Design and fabrication of highly open nickel cobalt sulfide nanosheets on Ni foam for asymmetric supercapacitors with high energy density and long cycle-life

NASA Astrophysics Data System (ADS)

Zha, Daosong; Fu, Yongsheng; Zhang, Lili; Zhu, Junwu; Wang, Xin

2018-02-01

Nickel cobalt sulfides (NiCo-S) are promising electrode materials for high-performance supercapacitors but normally show poor rate capability and unsatisfactory long-term endurance. To overcome these disadvantages, a properly constructed electrode architecture with abundant electron transport channels, excellent electronic conductivity and robust structural stability is required. Herein, considering that in situ transformation can mostly retain the specific structural advantages of the precursors, a two-step strategy is purposefully developed to construct a binder-free electrode composed of interconnected NiCo-S nanosheets on Ni foam (NiCo-S/NF), in which NiCo-S/NF is synthesized via the in situ sulfuration of networked acetate anion-intercalated nickel cobalt layered double hydroxide nanosheets loaded on Ni foam (A-NiCo-LDH/NF). Noticeably, the optimized Ni1Co1-S/NF exhibits an ultrahigh specific capacitance of 2553.9 F g-1 at 0.5 A g-1, excellent rate capability (1898.1 F g-1 at 50 A g-1) and superior cycling stability (nearly 90% capacitance retention after 10,000 cycles). Furthermore, the assembled asymmetric supercapacitor based on Ni1Co1-S/NF demonstrates a high energy density of 58.1 Wh kg-1 at a power density of 796 W kg-1 and impressive long-term durability even after a repeated charge/discharge process as long as 70,000 cycles (∼92% capacitance retention). The attractive properties endow the Ni1Co1-S/NF electrode with significant potential for high-performance energy storage devices.

Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid

NASA Astrophysics Data System (ADS)

Maluangnont, Tosapol; Arsa, Pornanan; Limsakul, Kanokporn; Juntarachairot, Songsit; Sangsan, Saithong; Gotoh, Kazuma; Sooknoi, Tawan

2016-06-01

While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Lihua; He, Xiaoman; Qu, Jun

Al(OH){sub 3} and Ca(OH){sub 2} powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kineticsmore » with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. - Graphical abstract: Activated Ca-Al hydroxides (C{sub 3}A) transformed into Ca-Al-OH compound when agitated in water. Ca-Al precursor (C{sub 3}A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO{sub 4} LDH product. Ca-Al-CrO{sub 4} LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. - Highlights: • Activated Ca-Al hydroxides transformed into LDH when agitated in water with some inorganic substances. • Hexavalent Cr was incorporated in the LDH structure at high adsorption capacity. • Ca-Al-Cr LDH phase occurred preferentially to Ca-Al-MCl{sub 2} LDH phases with coexistence. • The prepared Ca-Al hydroxides had high performance as adsorbent even with high salinity of the solution.« less

Increasing the Analytical Sensitivity by Oligonucleotides Modified with Para- and Ortho-Twisted Intercalating Nucleic Acids – TINA

PubMed Central

Schneider, Uffe V.; Géci, Imrich; Jøhnk, Nina; Mikkelsen, Nikolaj D.; Pedersen, Erik B.; Lisby, Gorm

2011-01-01

The sensitivity and specificity of clinical diagnostic assays using DNA hybridization techniques are limited by the dissociation of double-stranded DNA (dsDNA) antiparallel duplex helices. This situation can be improved by addition of DNA stabilizing molecules such as nucleic acid intercalators. Here, we report the synthesis of a novel ortho-Twisted Intercalating Nucleic Acid (TINA) amidite utilizing the phosphoramidite approach, and examine the stabilizing effect of ortho- and para-TINA molecules in antiparallel DNA duplex formation. In a thermal stability assay, ortho- and para-TINA molecules increased the melting point (Tm) of Watson-Crick based antiparallel DNA duplexes. The increase in Tm was greatest when the intercalators were placed at the 5′ and 3′ termini (preferable) or, if placed internally, for each half or whole helix turn. Terminally positioned TINA molecules improved analytical sensitivity in a DNA hybridization capture assay targeting the Escherichia coli rrs gene. The corresponding sequence from the Pseudomonas aeruginosa rrs gene was used as cross-reactivity control. At 150 mM ionic strength, analytical sensitivity was improved 27-fold by addition of ortho-TINA molecules and 7-fold by addition of para-TINA molecules (versus the unmodified DNA oligonucleotide), with a 4-fold increase retained at 1 M ionic strength. Both intercalators sustained the discrimination of mismatches in the dsDNA (indicated by ΔTm), unless placed directly adjacent to the mismatch – in which case they partly concealed ΔTm (most pronounced for para-TINA molecules). We anticipate that the presented rules for placement of TINA molecules will be broadly applicable in hybridization capture assays and target amplification systems. PMID:21673988

Structural and morphological characterization of Mg{sub 0.8}Al{sub 0.2}(OH){sub 2}Cl{sub 0.2} hydrotalcite produced by mechanochemistry method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fahami, Abbas, E-mail: fahami@txstate.edu; Beall, Gary W., E-mail: gb11@txstate.edu; Physics Department, Faculty of Science, King Abdulaziz University, Jeddah 21589

2016-01-15

Chlorine intercalated Mg–Al layered double hydroxides (Mg–Al–Cl–LDH) with a chemical formula Mg{sub 0.8}Al{sub 0.2}(OH){sub 2}Cl{sub 0.2} were successfully produced by the one-step mechanochemistry method and subsequent water washing followed by drying in oven for 1 h at 80 °C. The samples were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FT–IR), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), elemental mapping analysis, transmission electron microscopy (TEM), X-ray fluorescence (XRF), and the differential thermogravimetric analysis (DTGA). Results revealed that the structural characteristics of Mg–Al–Cl–LDH were affected strongly by milling time. At the beginning of milling (up to 1more » h), Hydrotalcite (HT) and Brucite were the dominant phases, while the progressive mechanical activation was completed as milling time increased, which resulted in the formation of nanostructured Mg–Al–Cl–LDH. Based on XRD and FTIR data, Mg{sub 0.8}Al{sub 0.2}(OH){sub 2}Cl{sub 0.2} with high purity was obtained at 5 h milling. The interlayer spacing of LDH is also strongly influenced by milling time so that it escalated from 7.737±0.001 to 8.005±0.002 (1–15 h) and then decreased to 7.937±0.001 for 20 h milled sample. Electron microscopic observation displayed that the final product had hexagonal platelet structure with lateral dimension of 20–100 nm. Therefore, the synthesis of Mg{sub 0.8}Al{sub 0.2}(OH){sub 2}Cl{sub 0.2} via mechanochemistry owing to simplicity and versatility can be a promising candidate for use in catalyst carriers, drug delivery, and gene delivery. - Graphical Abstract: TEM image of milled sample (Mg–Al–Cl–LDH). - Highlights: • Chlorine intercalated LDH was synthesized by a facile solid-state process. • Structural features of products were influenced strongly by the milling time. • XRD and FTIR spectra suggested predominant Mg–Al–Cl–LDH after 5 h milling. • Products showed hexagonal platelet structure with lateral dimension of 20–100 nm.« less

DNA Polyplexes as Combinatory Drug Carriers of Doxorubicin and Cisplatin: An In Vitro Study

PubMed Central

Kang, Han Chang; Cho, Hana; Bae, You Han

2015-01-01

Double helix nucleic acids were used as a combination drug carrier for doxorubicin (DOX), which physically intercalates with DNA double helices, and cisplatin (CDDP), which binds to DNA without an alkylation reaction. DNA interacting with DOX, CDDP, or both was complexed with positively charged, endosomolytic polymers. Compared with the free drug, the polyplexes (100 ~ 170 nm in size) delivered more drug into the cytosol and the nucleus and demonstrated similar or superior (up to a 7-fold increase) in vitro cell-killing activity. Additionally, the gene expression activities of most of the chemical drug-loaded plasmid DNA (pDNA) polyplexes were not impaired by the physical interactions between the nucleic acid and DOX/CDDP. When a model reporter pDNA (luciferase) was employed, it expressed luciferase protein at 0.7- ~ 1.4-fold the amount expressed by the polyplex with no bound drugs (a control), which indicated the fast translocation of the intercalated or bound drugs from the “carrier DNA” to the “nuclear DNA” of target cells. The proposed concept may offer the possibility of versatile combination therapies of genetic materials and small molecule drugs that bind to nucleic acids to treat various diseases. PMID:26132975

Nanogold-functionalized DNAzyme concatamers with redox-active intercalators for quadruple signal amplification of electrochemical immunoassay.

PubMed

Zhou, Jun; Lai, Wenqiang; Zhuang, Junyang; Tang, Juan; Tang, Dianping

2013-04-10

A novel and in situ amplified immunoassay strategy with quadruple signal amplification was designed for highly efficient electrochemical detection of low-abundance proteins (carcinoembryonic antigen, CEA, as a model) by using nanogold-functionalized DNAzyme concatamers with redox-active intercalators. To construct such an in situ amplification system, streptavidin-labeled gold nanoparticles (AuNP-SA) were initially used for the labelling of initiator strands (S0) and detection antibody (mAb2) with a large ratio (mAb2-AuNP-S0), and then two auxiliary DNA strands S1 and S2 were designed for in situ propagation of DNAzyme concatamers with the hemin/G-quadruplex format. The quadruple signal amplification was implemented by using the avidin-biotin chemistry, nanogold labels, DNA concatamers, and DNAzymes. In the presence of target CEA, the sandwiched immunocomplex was formed between the immobilized primary antibodies on the electrode and the conjugated detection antibodies on the mAb2-AuNP-S0. The carried S0 initiator strands could progress a chain reaction of hybridization events between alternating S1/S2 DNA strands to form a nicked double-helix. Upon addition of hemin, the hemin-binding aptamers could be bound to form the hemin/G-quadruplex-based DNAzymes. The formed double-helix DNA polymers could cause the intercalation of numerous electroactive methylene blue molecules. During the electrochemical measurement, the formed DNAzymes could catalyze the reduction of H2O2 in the solution to amplify the electrochemical signal of the intercalated methylene blue. Under optimal conditions, the electrochemical immunoassay exhibited a wide dynamic range of 1.0 fg mL(-1) to 20 ng mL(-1) toward CEA standards with a low detection limit of 0.5 fg mL(-1). Intra-assay and inter-assay coefficients of variation (CV) were less than 8.5% and 11.5%, respectively. No significant differences at the 0.05 significance level were encountered in the analysis of 14 clinical serum specimens between the developed immunoassay and commercialized electrochemiluminescent (ECL) method for detection of CEA.

Fabricating solid carbon porous electrodes from powders

DOEpatents

Kaschmitter, James L.; Tran, Tri D.; Feikert, John H.; Mayer, Steven T.

1997-01-01

Fabrication of conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive dionization, and waste treatment. Electrodes fabricated from low surface area (<50 m.sup.2 /gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon compositives with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to be high surface area carbons, fuel cell electrodes can be produced.

Fabricating solid carbon porous electrodes from powders

DOEpatents

Kaschmitter, J.L.; Tran, T.D.; Feikert, J.H.; Mayer, S.T.

1997-06-10

Fabrication is described for conductive solid porous carbon electrodes for use in batteries, double layer capacitors, fuel cells, capacitive deionization, and waste treatment. Electrodes fabricated from low surface area (<50 m{sup 2}/gm) graphite and cokes exhibit excellent reversible lithium intercalation characteristics, making them ideal for use as anodes in high voltage lithium insertion (lithium-ion) batteries. Electrodes having a higher surface area, fabricated from powdered carbon blacks, such as carbon aerogel powder, carbon aerogel microspheres, activated carbons, etc. yield high conductivity carbon composites with excellent double layer capacity, and can be used in double layer capacitors, or for capacitive deionization and/or waste treatment of liquid streams. By adding metallic catalysts to high surface area carbons, fuel cell electrodes can be produced. 1 fig.

Design of latex-layered double hydroxide composites by tuning the aggregation in suspensions.

PubMed

Pavlovic, Marko; Rouster, Paul; Bourgeat-Lami, Elodie; Prevot, Vanessa; Szilagyi, Istvan

2017-01-25

Colloidal stability of polymeric latex particles was studied in the presence of oppositely charged layered double hydroxide (LDH) platelets of different interlayer anions. Adsorption of the LDH particles led to charge neutralization and to overcharging of the latex at appropriate concentrations. Mixing stable colloidal suspensions of individual particles results in rapid aggregation once the LDH adsorption neutralizes the negative charges of the polymer spheres, while stable suspensions were observed at high and low LDH doses. The governing interparticle interactions included repulsive electrical double layer forces as well as van der Waals and patch-charge attractions, whose strength depended on the amount of LDH particles adsorbed on the latex surface. The type of the LDH interlayer anions did not affect the colloidal stability of the samples. Structural investigation of the obtained latex-LDH composites revealed that the polymer spheres were completely coated with the inorganic platelets once their concentration was sufficiently high. These results are especially important for designing synthetic routes for hybrid systems in suspensions, where stable colloids are required for uniform film-formation and for the homogeneous distribution of the inorganic filler within the composite materials.

Transformation of Chlorinated Hydrocarbons on Synthetic Green Rusts

EPA Science Inventory

Green rusts (GRs) are layered double hydroxides that contain both ferrous and ferric ions in their structure. GRs can potentially serve as a chemical reductant for degradation of chlorinated hydrocarbons. GRs are found in zerovalent iron based permeable reactive barriers and in c...

Monolayer atomic crystal molecular superlattices.

PubMed

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A; Huang, Yu; Duan, Xiangfeng

2018-03-07

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 10 7 , along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

Monolayer atomic crystal molecular superlattices

NASA Astrophysics Data System (ADS)

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O.; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A., III; Huang, Yu; Duan, Xiangfeng

2018-03-01

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

PubMed

Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

2018-03-21

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

First-principles estimates of free energy barriers for Mg desolvation and intercalation at electrolyte/electrode interfaces

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2014-03-01

There is a growing interest in developing multivalent ion batteries that could, in principle, double or triple the energy density compared to the monovalent Li-ion batteries. However, the strong electrostatic interaction caused by the extra charge also makes it very challenging to find appropriate intercalation compounds that allow for relatively fast and reversible ion transport. An established working multivalent battery is comprised of Mg(AlCl2BuEt)2 salts in THF solution as the electrolyte, and Mg metal and Mo6S8 Chevrel phase as the anode and cathode, respectively. Currently, we lack a clear understanding of the mechanism for Mg desolvation and intercalation at the interface between the electrolyte and Chevrel phase surfaces, which is critical in designing new advanced battery systems with improved ion diffusion rate. Here, we present a theoretical investigation of the dynamics and kinetics of the Mg desolvation/intercalation process. The surface properties of Mo6S8 are studied for the first time using density functional theory (DFT) and its interaction with the electrolyte is simulated via an ab initio molecular dynamics (AIMD) approach. The free energy barrier for Mg diffusing through the interface is then calculated by performing a set of biased AIMD simulations. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

DOUBLE SHELL TANK (DST) INTEGRITY PROJECT HIGH LEVEL WASTE CHEMISTRY OPTIMIZATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

WASHENFELDER DJ

2008-01-22

The U.S. Department of Energy's Office (DOE) of River Protection (ORP) has a continuing program for chemical optimization to better characterize corrosion behavior of High-Level Waste (HLW). The DOE controls the chemistry in its HLW to minimize the propensity of localized corrosion, such as pitting, and stress corrosion cracking (SCC) in nitrate-containing solutions. By improving the control of localized corrosion and SCC, the ORP can increase the life of the Double-Shell Tank (DST) carbon steel structural components and reduce overall mission costs. The carbon steel tanks at the Hanford Site are critical to the mission of safely managing stored HLWmore » until it can be treated for disposal. The DOE has historically used additions of sodium hydroxide to retard corrosion processes in HLW tanks. This also increases the amount of waste to be treated. The reactions with carbon dioxide from the air and solid chemical species in the tank continually deplete the hydroxide ion concentration, which then requires continued additions. The DOE can reduce overall costs for caustic addition and treatment of waste, and more effectively utilize waste storage capacity by minimizing these chemical additions. Hydroxide addition is a means to control localized and stress corrosion cracking in carbon steel by providing a passive environment. The exact mechanism that causes nitrate to drive the corrosion process is not yet clear. The SCC is less of a concern in the newer stress relieved double shell tanks due to reduced residual stress. The optimization of waste chemistry will further reduce the propensity for SCC. The corrosion testing performed to optimize waste chemistry included cyclic potentiodynamic volarization studies. slow strain rate tests. and stress intensity factor/crack growth rate determinations. Laboratory experimental evidence suggests that nitrite is a highly effective:inhibitor for pitting and SCC in alkaline nitrate environments. Revision of the corrosion control strategies to a nitrite-based control, where there is no constant depletion mechanism as with hydroxide, should greatly enhance tank lifetime, tank space availability, and reduce downstream reprocessing costs by reducing chemical addition to the tanks.« less

Wearable Fabrics with Self-Branched Bimetallic Layered Double Hydroxide Coaxial Nanostructures for Hybrid Supercapacitors.

PubMed

Nagaraju, Goli; Chandra Sekhar, S; Krishna Bharat, L; Yu, Jae Su

2017-11-28

We report a flexible battery-type electrode based on binder-free nickel cobalt layered double hydroxide nanosheets adhered to nickel cobalt layered double hydroxide nanoflake arrays on nickel fabric (NC LDH NFAs@NSs/Ni fabric) using facile and eco-friendly synthesis methods. Herein, we utilized discarded polyester fabric as a cost-effective substrate for in situ electroless deposition of Ni, which exhibited good flexibility, light weight, and high conductivity. Subsequently, the vertically aligned NC LDH NFAs were grown on Ni fabric by means of a hot-air oven-based method, and fluffy-like NC LDH NS branches are further decorated on NC LDH NFAs by a simple electrochemical deposition method. The as-prepared core-shell-like nanoarchitectures improve the specific surface area and electrochemical activity, which provides the ideal pathways for electrolyte diffusion and charge transportation. When the electrochemical performance was tested in 1 M KOH aqueous solution, the core-shell-like NC LDH NFAs@NSs/Ni fabric electrode liberated a maximum areal capacity of 536.96 μAh/cm 2 at a current density of 2 mA/cm 2 and excellent rate capability of 78.3% at 30 mA/cm 2 (420.5 μAh/cm 2 ) with a good cycling stability. Moreover, a fabric-based hybrid supercapacitor (SC) was assembled, which achieves a stable operational potential window of 1.6 V, a large areal capacitance of 1147.23 mF/cm 2 at 3 mA/cm 2 , and a high energy density of 0.392 mWh/cm 2 at a power density of 2.353 mW/cm 2 . Utilizing such high energy storage abilities and flexible properties, the fabricated hybrid SC operated the wearable digital watch and electric motor fan for real-time applications.

Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh

2016-01-15

A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less

Construction of hierarchically porous graphitized carbon-supported NiFe layered double hydroxides with a core-shell structure as an enhanced electrocatalyst for the oxygen evolution reaction.

PubMed

Ni, Yuanman; Yao, Lihua; Wang, Yin; Liu, Bing; Cao, Minhua; Hu, Changwen

2017-08-17

The oxygen evolution reaction (OER) is a vital half-reaction in water splitting and metal-air batteries. Developing earth-abundant, highly efficient and durable OER catalysts has faced huge challenges until now, because OER is a strict kinetic sluggish process. Herein, we report the construction of hierarchically porous graphitized carbon (HPGC) supported NiFe layered double hydroxides (LDHs) with a core-shell structure (denoted as HPGC@NiFe) by a facile strategy. The HPGC was first obtained by pyrolysing phenolic resin nanospheres with FeCl 3 and ZnCl 2 as the catalyst and the activator, respectively. Then the NiFe LDH arrays were directly grown on the HPGC by a one-step hydrothermal method. The as-synthesized HPGC@NiFe reveals excellent OER properties with a low onset potential, a lower overpotential of 265 mV (corresponding to the current density at 10 mA cm -2 ) and a small Tafel slope (56 mV per decade). And its catalytic activity is even superior to that of the start-of-the-art noble-metal catalyst IrO 2 /C. Notably, the HPGC@NiFe electrode shows admirable stability measured by performing 2000 cycle CVs and long-term electrolysis for 50 h. The prominent performance can be attributed to the synergistic effect between the NiFe-LDHs and the hierarchically porous graphitized carbon, in which the former can increase the exposure of the active sites, while the latter can increase the charge transfer efficiency. Our research implies the possibility for the development of low-cost layered double hydroxides as a promising candidate in electrochemical energy storage and conversion equipment.

Photocatalytic property and structural stability of CuAl-based layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lv, Ming; Liu, Haiqiang, E-mail: Liuhaiqiang1980@126.com

2015-07-15

Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) were successfully synthesized by coprecipitation. Powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-AES) and UV–Vis diffuse reflectance spectrum (UV–vis) were used to confirm the formation of as-synthesized solids with good crystal structure. The photocatalytic activity of those LDH materials for CO{sub 2} reduction under visible light was investigated. The experimental results show that CuNiAl-LDHs with narrowest band gap and largest surface areas behave highest efficiency for methanol generation under visible light compared with CuMgAl-LDHs and CuZnAl-LDHs. The CuNiAL-LDH showed high yield for methanol production i.e. 0.210more » mmol/g h, which was high efficient. In addition, the influence of the different M{sup 2+} on the structures and stability of the CuMAl-LDHs was also investigated by analyzing the geometric parameters, electronic arrangement, charge populations, hydrogen-bonding, and binding energies by density functional theory (DFT) analysis. The theoretical calculation results show that the chemical stability of LDH materials followed the order of CuMgAl-LDHs>CuZnAl-LDHs>CuNiAl-LDHs, which is just opposite with the photocatalytic activity and band gaps of three materials. - Graphical abstract: The host–guest calculation models and XRD patterns of CuMAl-LDHs: CuMgAl-LDHs (a), CuZnAl-LDHs (b) and CuNiAl-LDHs (c). - Highlights: • Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) has been synthesized. • CuMgNi shows narrower band gap and more excellent textural properties than other LDHs. • The band gap: CuMgAl« less

Layered double hydroxide materials coated carbon electrode: New challenge to future electrochemical power devices

NASA Astrophysics Data System (ADS)

Djebbi, Mohamed Amine; Braiek, Mohamed; Namour, Philippe; Ben Haj Amara, Abdesslem; Jaffrezic-Renault, Nicole

2016-11-01

Layered double hydroxides (LDHs) have been widely used in the past years due to their unique physicochemical properties and promising applications in electroanalytical chemistry. The present paper is going to focus exclusively on magnesium-aluminum and zinc-aluminum layered double hydroxides (MgAl & ZnAl LDHs) in order to investigate the property and structure of active cation sites located within the layer structure. The MgAl and ZnAl LDH nanosheets were prepared by the constant pH co-precipitation method and uniformly supported on carbon-based electrode materials to fabricate an LDH electrode. Characterization by powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy revealed the LDH form and well-crystallized materials. Wetting surface properties (hydrophilicity and hydrophobicity) of both prepared LDHs were recorded by contact angle measurement show hydrophilic character and basic property. The electrochemical performance of these hybrid materials was investigated by mainly cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques to identify the oxidation/reduction processes at the electrode/electrolyte interface and the effect of the divalent metal cations in total reactivity. The hierarchy of the modified electrode proves that the electronic conductivity of the bulk material is considerably dependent on the divalent cation and affects the limiting parameter of the overall redox process. However, MgAl LDH shows better performance than ZnAl LDH, due to the presence of magnesium cations in the layers. Following the structural, morphological and electrochemical behavior studies of both synthesized LDHs, the prepared LDH modified electrodes were tested through microbial fuel cell configuration, revealing a remarkable, potential new pathway for high-performance and cost-effective electrode use in electrochemical power devices.

Adsorption of charged protein residues on an inorganic nanosheet: Computer simulation of LDH interaction with ion channel

NASA Astrophysics Data System (ADS)

Tsukanov, Alexey A.; Psakhie, Sergey G.

2016-08-01

Quasi-two-dimensional and hybrid nanomaterials based on layered double hydroxides (LDH), cationic clays, layered oxyhydroxides and hydroxides of metals possess large specific surface area and strong electrostatic properties with permanent or pH-dependent electric charge. Such nanomaterials may impact cellular electrostatics, changing the ion balance, pH and membrane potential. Selective ion adsorption/exchange may alter the transmembrane electrochemical gradient, disrupting potential-dependent cellular processes. Cellular proteins as a rule have charged residues which can be effectively adsorbed on the surface of layered hydroxide based nanomaterials. The aim of this study is to attempt to shed some light on the possibility and mechanisms of protein "adhesion" an LDH nanosheet and to propose a new direction in anticancer medicine, based on physical impact and strong electrostatics. An unbiased molecular dynamics simulation was performed and the combined process free energy estimation (COPFEE) approach was used.

Efficient carbon dots/NiFe-layered double hydroxide/BiVO4 photoanodes for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Lv, Xiaowei; Xiao, Xin; Cao, Minglei; Bu, Yi; Wang, Chuanqing; Wang, Mingkui; Shen, Yan

2018-05-01

Modification of semiconductor photoanodes with oxygen evolution catalyst (OEC) is an effective approach for improving photoelectrochemical (PEC) water splitting efficiency. In the configuration, how to increase the activity of OEC is crucial to further improve PEC performance. Herein, a ternary photoanode system was designed to enhance PEC efficiency of photoelectrodes through introducing carbon dots (CDs), NiFe-layered double hydroxide (NiFe-LDH) nanosheets on BiVO4 particles. Systematic research shows that NiFe-LDH serves as an OEC which accelerates oxygen evolution kinetics, while the introduction of CDs can further reduce charge transfer resistance and overpotential for oxygen evolution. Under the synergistic effect of NiFe-LDH and CDs, the photocurrent and incident photon to current conversion efficiency (IPCE) of the resulting CDs/NiFe-LDH/BiVO4 photoanode is improved significantly than those of the NiFe-LDH/BiVO4 electrode. Consequently, such a ternary heterostructure could be an alternative way to further enhance PEC water splitting performance.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhao; Zhou, Daojin; Wang, Maoyu

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

New Insights into CO2 Adsorption on Layered Double Hydroxide (LDH)-Based Nanomaterials

NASA Astrophysics Data System (ADS)

Tang, Nian; He, Tingyu; Liu, Jie; Li, Li; Shi, Han; Cen, Wanglai; Ye, Zhixiang

2018-02-01

The interlamellar spacing of layered double hydroxides (LDHs) was enlarged by dodecyl sulfonate ions firstly, and then, (3-aminopropyl)triethoxysilane (APS) was chemically grafted (APS/LDHs). The structural characteristics and thermal stability of these prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), reflectance Fourier transform infrared spectrometer (FTIR), thermogravimetric analysis (TG), and elemental analysis (EA) respectively. The CO2 adsorption performance was investigated adopting TG and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results presented that the CO2 adsorption capacity on APS/LDHs was as high as 90 mg/g and showed no obvious reduction during a five cyclic adsorption-desorption test, indicating its superior performance stability. The DRIFTS results showed that both carbamates and weakly bounded CO2 species were generated on APS/LDHs. The weakly adsorbed species was due to the different local chemical environment for CO2 capture provided by the surface moieties of LDHs like free silanol and hydrogen bonds.

Three-dimensional porous MXene/layered double hydroxide composite for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Ya; Dou, Hui; Wang, Jie; Ding, Bing; Xu, Yunling; Chang, Zhi; Hao, Xiaodong

2016-09-01

In this work, an exfoliated MXene (e-MXene) nanosheets/nickel-aluminum layered double hydroxide (MXene/LDH) composite as supercapacitor electrode material is fabricated by in situ growth of LDH on e-MXene substrate. The LDH platelets homogeneously grown on the surface of the e-MXene sheets construct a three-dimensional (3D) porous structure, which not only leads to high active sites exposure of LDH and facile liquid electrolyte penetration, but also alleviates the volume change of LDH during the charge/discharge process. Meanwhile, the e -MXene substrate forms a conductive network to facilitate the electron transport of active material. The optimized MXene/LDH composite exhibits a high specific capacitance of 1061 F g-1 at a current density of 1 A g-1, excellent capacitance retention of 70% after 4000 cycle tests at a current density of 4 A g-1 and a good rate capability with 556 F g-1 retention at 10 A g-1.

Fabrication of hierarchical core-shell polydopamine@MgAl-LDHs composites for the efficient enrichment of radionuclides

NASA Astrophysics Data System (ADS)

Zhu, Kairuo; Lu, Songhua; Gao, Yang; Zhang, Rui; Tan, Xiaoli; Chen, Changlun

2017-02-01

Novel hierarchical core/shell structured polydopamine@MgAl-layered double hydroxides (PDA@MgAl-LDHs) composites involving MgAl-layered double hydroxide shells and PDA cores were fabricated thought one-pot coprecipitation assembly and methodically characterized by X-ray diffraction, Fourier transformed infrared spectroscopy, scanning/transmission electron microscopy, selected area electron diffraction, elemental mapping, thermogravimetric analysis and X-ray photoelectron spectroscopy technologies. U(VI) and Eu(III) sorption experiments showed that the PDA@MgAl-LDHs exhibited higher sorption ability with a maximum sorption capacity of 142.86 and 76.02 mg/g at 298 K and pH 4.5, respectively. More importantly, according to XPS analyses, U(VI) and Eu(III) were sorbed on PDA@MgAl-LDHs via oxygen-containing functional groups, and the chemical affinity of U(VI) by oxygen-containing functional groups is higher than that of Eu(III). These observations show great expectations in the enrichment of radionuclides from aquatic environments by PDA@MgAl-LDHs.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites.

PubMed

Nedim Ay, Ahmet; Konuk, Deniz; Zümreoglu-Karan, Birgul

2011-02-03

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules.

Prolate spheroidal hematite particles equatorially belt with drug-carrying layered double hydroxide disks: Ring Nebula-like nanocomposites

PubMed Central

2011-01-01

A new nanocomposite architecture is reported which combines prolate spheroidal hematite nanoparticles with drug-carrying layered double hydroxide [LDH] disks in a single structure. Spindle-shaped hematite nanoparticles with average length of 225 nm and width of 75 nm were obtained by thermal decomposition of hydrothermally synthesized hematite. The particles were first coated with Mg-Al-NO3-LDH shell and then subjected to anion exchange with salicylate ions. The resulting bio-nanohybrid displayed a close structural resemblance to that of the Ring Nebula. Scanning electron microscope and transmission electron microscopy images showed that the LDH disks are stacked around the equatorial part of the ellipsoid extending along the main axis. This geometry possesses great structural tunability as the composition of the LDH and the nature of the interlayer region can be tailored and lead to novel applications in areas ranging from functional materials to medicine by encapsulating various guest molecules. PMID:21711652

Calcined Mg-Fe layered double hydroxide as an absorber for the removal of methyl orange

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Chao; State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070; Dai, Jing

2015-05-15

In this work, methyl orange (MO) was effectively removed from aqueous solution with the calcined product of hydrothermal synthesized Mg/Fe layered double hydroxide (Mg/Fe-LDH). The structure, composition, morphology and textural properties of the Mg/Fe-LDH before and after adsorption were characterized by X-ray diffraction, Fourier transformation infrared spectroscopy, transmission electron microscopy, nitrogen adsorption apparatus and X-ray photoelectron spectroscopy. It was confirmed that MO had been absorbed by calcined Mg/Fe-LDH which had strong interactions with MO. The adsorption of MO onto the Mg/Fe-LDH was systematically investigated by batch tests. The adsorption capacity of the Mg/Fe-LDH toward MO was found to be 194.9more » mg • g{sup −1}. Adsorption kinetics and isotherm studies revealed that the adsorption of MO onto Mg/Fe-LDH was a spontaneous and endothermic process. These results indicate that Mg/Fe-LDH is a promising material for the removal of MO.« less

Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

PubMed

Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

2016-05-24

Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

Systemic toxicity induced by aggregated layered double hydroxide nanoparticles

PubMed Central

Yan, Mina; Yang, Chanzhen; Huang, Binyao; Huang, Zeqian; Huang, Liangfeng; Zhang, Xuefei; Zhao, Chunshun

2017-01-01

Layered double hydroxide (LDH) nanoparticles are emerging as one of the promising nanomaterials for biomedical applications, but their systemic toxicity in vivo has received little attention. In the present study, the effects of inorganic nanoparticle aggregation on their systemic toxicity were examined. Remarkably, aggregation was observed after the mixing of naked LDH nanoparticles with saline or erythrocytes. Significant accumulation of the naked LDH nanoparticles in the lungs of mice was detected 1 h after intravenous administration, and the survival rate of mice was 0% after 6 repeated injections. Furthermore, flocculent precipitates in the alveoli and congestion in the lung interstitium were observed in the dead mice. However, lipid membrane-coated LDH nanoparticles would not form aggregates and could be injected intravenously >6 times without causing death. These findings suggested that repeated injections of LDH were lethal even at low dose (30 mg/kg), and lipid membrane coating can be considered as an approach for reducing this risk. PMID:29042768

Deconstruction of Lignin Model Compounds and Biomass-Derived Lignin using Layered Double Hydroxide Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chmely, S. C.; McKinney, K. A.; Lawrence, K. R.

2013-01-01

Lignin is an underutilized value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading. Base-catalyzed deconstruction (BCD) has been applied for lignin depolymerization (e.g., the Kraft process) in the pulp and paper industry for more than a century using aqueous-phase media. However, these efforts require treatment to neutralize the resulting streams, which adds significantly to the cost of lignin deconstruction. To circumvent the need for downstream treatment, here we report recent advances in the synthesis of layered double hydroxide and metal oxide catalysts to be applied to the BCDmore » of lignin. These catalysts may prove more cost-effective than liquid-phase, non-recyclable base, and their use obviates downstream processing steps such as neutralization. Synthetic procedures for various transition-metal containing catalysts, detailed kinetics measurements using lignin model compounds, and results of the application of these catalysts to biomass-derived lignin will be presented.« less

Corrosion resistance of Zn-Al layered double hydroxide/poly(lactic acid) composite coating on magnesium alloy AZ31

NASA Astrophysics Data System (ADS)

Zeng, Rong-Chang; Li, Xiao-Ting; Liu, Zhen-Guo; Zhang, Fen; Li, Shuo-Qi; Cui, Hong-Zhi

2015-12-01

A Zn-Al layered double hydroxide (ZnAl-LDH) coating consisted of uniform hexagonal nano-plates was firstly synthesized by co-precipitation and hydrothermal treatment on the AZ31 alloy, and then a poly(lactic acid) (PLA) coating was sealed on the top layer of the ZnAl-LDH coating using vacuum freeze-drying. The characteristics of the ZnAl-LDH/PLA composite coatings were investigated by means of XRD, SEM, FTIR and EDS. The corrosion resistance of the coatings was assessed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the ZnAl-LDH coating contained a compact inner layer and a porous outer layer, and the PLA coating with a strong adhesion to the porous outer layer can prolong the service life of the ZnAl-LDH coating. The excellent corrosion resistance of this composite coating can be attributable to its barrier function, ion-exchange and self-healing ability.

Introducing Fe2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity.

PubMed

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; Bak, Seongmin; Wu, Yueshen; Wu, Zishan; Tian, Yang; Xiong, Xuya; Li, Yaping; Liu, Wen; Siahrostami, Samira; Kuang, Yun; Yang, Xiao-Qing; Duan, Haohong; Feng, Zhenxing; Wang, Hailiang; Sun, Xiaoming

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel-iron layered double hydroxides (NiFe-LDHs) by partially substituting Ni2+ with Fe2+ to introduce Fe-O-Fe moieties. These Fe2+-containing NiFe-LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm2, which is among the best OER catalytic performance reported to date. In-situ X-ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe-O-Fe motifs could stabilize high-valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Introducing Fe 2+ into Nickel-Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

DOE PAGES

Cai, Zhao; Zhou, Daojin; Wang, Maoyu; ...

2018-06-11

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Here we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe–LDHs) by partially substituting Ni 2+ with Fe 2+ to introduce Fe–O–Fe moieties. These Fe 2+–containing NiFe–LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA/cm 2, which is among the best OER catalytic performance reported to date. In–situ X–ray absorption, Raman, and electrochemical analysis jointlymore » reveal that the Fe–O–Fe motifs could stabilize high–valent metal sites at low overpotentials, thereby enhancing the OER activity. Lastly, these results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.« less

Transesterification of edible, non-edible and used cooking oils for biodiesel production using calcined layered double hydroxides as reusable base catalysts.

PubMed

Sankaranarayanan, Sivashunmugam; Antonyraj, Churchil A; Kannan, S

2012-04-01

Fatty acid methyl esters (FAME) were produced from edible, non-edible and used cooking oils with different fatty acid contents by transesterification with methanol using calcined layered double hydroxides (LDHs) as solid base catalysts. Among the catalysts, calcined CaAl2-LDH (hydrocalumite) showed the highest activity with >90% yield of FAME using low methanol:oil molar ratio (<6:1) at 65 °C in 5 h. The activity of the catalyst was attributed to its high basicity as supported by Hammett studies and CO(2)-TPD measurements. The catalyst was successfully reused in up to four cycles. Some of the properties such as density, viscosity, neutralization number and glycerol content of the obtained biodiesel matched well with the standard DIN values. It is concluded that a scalable heterogeneously catalyzed process for production of biodiesel in high yields from a wide variety of triglyceride oils including used oils is possible using optimized conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Durability of nickel-metal hydride (Ni-MH) battery cathode using nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite

NASA Astrophysics Data System (ADS)

Béléké, Alexis Bienvenu; Higuchi, Eiji; Inoue, Hiroshi; Mizuhata, Minoru

2014-02-01

We report the durability of the optimized nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite prepared by liquid phase deposition (LPD) as cathode active materials in nickel metal hydride (Ni-MH) secondary battery. The positive electrode was used for charge-discharge measurements under two different current: 5 mA for 300 cycles in half-cell conditions, and 5.8 mA for 569 cycles in battery regime, respectively. The optimized Ni-Al LDH/C composite exhibits a good lifespan and stability with the capacity retention above 380 mA h gcomp-1 over 869 cycles. Cyclic voltammetry shows that the α-Ni(OH)2/γ-NiOOH redox reaction is maintained even after 869 cycles, and the higher current regime is beneficial in terms of materials utilization. X-ray diffraction (XRD) patterns of the cathode after charge and discharge confirms that the α-Ni(OH)2/γ-NiOOH redox reaction occurs without any intermediate phase.

The Adsorption of Dextranase onto Mg/Fe-Layered Double Hydroxide: Insight into the Immobilization

PubMed Central

Ding, Yi; Liu, Le; Fang, Yaowei; Zhang, Xu; Lyu, Mingsheng; Wang, Shujun

2018-01-01

We report the adsorption of dextranase on a Mg/Fe-layered double hydroxide (Mg/Fe-LDH). We focused the effects of different buffers, pH, and amino acids. The Mg/Fe-LDH was synthesized, and adsorption experiments were performed to investigate the effects. The maximum adsorption occurred in pH 7.0 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, and the maximum dextranase adsorption uptake was 1.38 mg/g (416.67 U/mg); histidine and phenylalanine could affect the adsorption. A histidine tag could be added to the protein to increase the adsorption significantly. The performance features and mechanism were investigated with X-ray diffraction patterns (XRD) and Fourier transform infrared spectra (FTIR). The protein could affect the crystal structure of LDH, and the enzyme was adsorbed on the LDH surface. The main interactions between the protein and LDH were electrostatic and hydrophobic. Histidine and phenylalanine could significantly affect the adsorption. The hexagonal morphology of LDH was not affected after adsorption. PMID:29562655

Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides

NASA Astrophysics Data System (ADS)

García-García, J. M.; Pérez-Bernal, M. E.; Ruano-Casero, R. J.; Rives, V.

2007-12-01

Layered double hydroxides with the hydrotalcite-like structures, containing Mg 2+ and Al 3+, doped with Cr 3+ and Y 3+, have been prepared by precipitation at constant pH. The weight percentages of Cr 3+ and Y 3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV-vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at -196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE - L∗a∗b∗) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments.

Modified hydrotalcite-like compounds as active fillers of biodegradable polymers for drug release and food packaging applications.

PubMed

Costantino, Umberto; Nocchetti, Morena; Tammaro, Loredana; Vittoria, Vittoria

2012-11-01

This review treats the recent patents and related literature, mainly from the Authors laboratories, on biomedical and food packaging applications of nano-composites constituted of biodegradable polymers filled with micro or nano crystals of organically modified Layered Double Hydroxides of Hydrotalcite type. After a brief outline of the chemical and structural aspects of Hydrotalcite-like compounds (HTlc) and of their manipulation via intercalation of functional molecular anions to obtain materials for numerous, sometime unexpected applications, the review approaches the theme in three separated parts. Part 1 deals with the synthetic method used to prepare the pristine Mg-Al and Zn-Al HTlc and with the procedures of their functionalization with anti-inflammatory (diclofenac), antibacterial (chloramphenicol hemisuccinate), antifibrinolytic (tranexamic acid) drugs and with benzoates with antimicrobial activity. Procedures used to form (nano) composites of polycaprolactone, used as an example of biodegradable polymer, and functionalized HTlc are also reported. Part 2 discusses a patent and related papers on the preparation and biomedical use of a controlled delivery system of the above mentioned pharmacologically active substances. After an introduction dealing with the recent progress in the field of local drug delivery systems, the chemical and structural aspects of the patented system constituted of a biodegradable polymer and HTlc loaded with the active substances will be presented together with an extensive discussion of the drug release in physiological medium. Part 3 deals with a recent patent and related papers on chemical, structural and release property of antimicrobial species of polymeric films containing antimicrobial loaded HTlc able to act as active packaging for food products prolonging their shelf life.

Sonochemical surface functionalization of exfoliated LDH: Effect on textural properties, CO2 adsorption, cyclic regeneration capacities and subsequent gas uptake for simultaneous methanol synthesis.

PubMed

Ezeh, Collins I; Huang, Xiani; Yang, Xiaogang; Sun, Cheng-Gong; Wang, Jiawei

2017-11-01

To improve CO 2 adsorption, amine modified Layered double hydroxide (LDH) were prepared via a two stage process, SDS/APTS intercalation was supported by ultrasonic irradiation and then followed by MEA extraction. The prepared samples were characterised using Scanning electron microscope-Energy dispersive X-ray spectroscopy (SEM-EDX), X-ray Photoelectron Spectroscopy (XPS), X-ray diffraction (XRD), Temperature Programmed Desorption (TPD), Brunauer-Emmett-Teller (BET), and Thermogravimetric analysis (TGA), respectively. The characterisation results were compared with those obtained using the conventional preparation method with consideration to the effect of sonochemical functionalization on textural properties, adsorption capacity, regeneration and lifetime of the LDH adsorbent. It is found that LDHs prepared by sonochemical modification had improved pore structure and CO 2 adsorption capacity, depending on sonic intensity. This is attributed to the enhanced deprotonation of activated amino functional groups via the sonochemical process. Subsequently, this improved the amine loading and effective amine efficiency by 60% of the conventional. In addition, the sonochemical process improved the thermal stability of the adsorbent and also, reduced the irreversible CO 2 uptake, CUirrev, from 0.18mmol/g to 0.03mmol/g. Subsequently, improving the lifetime and ease of regenerating the adsorbent respectively. This is authenticated by subjecting the prepared adsorbents to series of thermal swing adsorption (TSA) cycles until its adsorption capacity goes below 60% of the original CO 2 uptake. While the conventional adsorbent underwent a 10 TSA cycles before breaking down, the sonochemically functionalized LDH went further than 30 TSA cycles. Copyright © 2017 Elsevier B.V. All rights reserved.

Major versus minor groove DNA binding of a bisarginylporphyrin hybrid molecule: A molecular mechanics investigation

NASA Astrophysics Data System (ADS)

Gresh, Nohad; Perrée-fauvet, Martine

1999-03-01

On the basis of theoretical computations, we have recently synthesised [Perrée-Fauvet, M. and Gresh, N., Tetrahedron Lett., 36 (1995) 4227] a bisarginyl conjugate of a tricationic porphyrin (BAP), designed to target, in the major groove of DNA, the d(GGC GCC)2 sequence which is part of the primary binding site of the HIV-1 retrovirus site [Wain-Hobson, S. et al., Cell, 40 (1985) 9]. In the theoretical model, the chromophore intercalates at the central d(CpG)2 step and each of the arginyl arms targets O6/N7belonging to guanine bases flanking the intercalation site. Recent IR and UV-visible spectroscopic studies have confirmed the essential features of these theoretical predictions [Mohammadi, S. et al., Biochemistry, 37 (1998) 6165]. In the present study, we compare the energies of competing intercalation modes of BAP to several double-stranded oligonucleotides, according to whether one, two or three N- methylpyridinium rings project into the major groove. Correspondingly, three minor groove binding modes were considered, the arginyl arms now targeting N3, O2 sites belonging to the purine or pyrimidine bases flanking the intercalation site. This investigation has shown that: (i) in both the major and minor grooves, the best-bound complexes have the three N-methylpyridinium rings in the groove opposite to that of the phenyl group bearing the arginyl arms; (ii) major groove binding is preferred over minor groove binding by a significant energy (29 kcal/mol); and (iii) the best-bound sequence in the major groove is d(GGC GCC)2 with two successive guanines upstream from the intercalation. On the other hand, due to the flexibility of the arginyl arms, other GC-rich sequences have close binding energies, two of them being less stable than it by less than 8 kcal/mol. These results serve as the basis for the design of derivatives of BAP with enhanced sequence selectivities in the major groove.

A green method of graphene preparation in an alkaline environment.

PubMed

Štengl, Václav; Henych, Jiří; Bludská, Jana; Ecorchard, Petra; Kormunda, Martin

2015-05-01

We present a new, simple, quick and ecologically friendly method of exfoliating graphite to produce graphene. The method is based on the intercalation of a permanganate M2MnO4 (M=K, Na, Li), which is formed by the reaction of a manganate MMnO4 with an alkali metal hydroxide MOH. The quality of exfoliation and the morphology were determined using X-ray photoelectron spectroscopy, X-ray diffraction and microscopic techniques, including transmission electron microscopy and atomic force microscopy. We observed that a stable graphene suspension could be prepared under strongly alkaline conditions in the presence of permanganate and ultrasound assistance. The use of only an alkaline environment for the direct preparation of graphene from graphite structures has not been previously described or applied. It was found that such a method of preparation leads to surprisingly high yields and a stable product for hydrophilic graphene applications. Copyright © 2014 Elsevier B.V. All rights reserved.

A facile electrochemical intercalation and microwave assisted exfoliation methodology applied to screen-printed electrochemical-based sensing platforms to impart improved electroanalytical outputs.

PubMed

Pierini, Gastón D; Foster, Christopher W; Rowley-Neale, Samuel J; Fernández, Héctor; Banks, Craig E

2018-06-12

Screen-printed electrodes (SPEs) are ubiquitous with the field of electrochemistry allowing researchers to translate sensors from the laboratory to the field. In this paper, we report an electrochemically driven intercalation process where an electrochemical reaction uses an electrolyte as a conductive medium as well as the intercalation source, which is followed by exfoliation and heating/drying via microwave irradiation, and applied to the working electrode of screen-printed electrodes/sensors (termed EDI-SPEs) for the first time. This novel methodology results in an increase of up to 85% of the sensor area (electrochemically active surface area, as evaluated using an outer-sphere redox probe). Upon further investigation, it is found that an increase in the electroactive area of the EDI-screen-printed based electrochemical sensing platforms is critically dependent upon the analyte and its associated electrochemical mechanism (i.e. adsorption vs. diffusion). Proof-of-concept for the electrochemical sensing of capsaicin, a measure of the hotness of chillies and chilli sauce, within both model aqueous solutions and a real sample (Tabasco sauce) is demonstrated in which the electroanalytical sensitivity (a plot of signal vs. concentration) is doubled when utilising EDI-SPEs over that of SPEs.

Photoinduced Oxidative DNA Damage Revealed by an Agarose Gel Nicking Assay: A Biophysical Chemistry Laboratory Experiment

NASA Astrophysics Data System (ADS)

Shafirovich, Vladimir; Singh, Carolyn; Geacintov, Nicholas E.

2003-11-01

Oxidative damage of DNA molecules associated with electron-transfer reactions is an important phenomenon in living cells, which can lead to mutations and contribute to carcinogenesis and the aging processes. This article describes the design of several simple experiments to explore DNA damage initiated by photoinduced electron-transfer reactions sensitized by the acridine derivative, proflavine (PF). A supercoiled DNA agarose gel nicking assay is employed as a sensitive probe of DNA strand cleavage. A low-cost experimental and computer-interfaced imaging apparatus is described allowing for the digital recording and analysis of the gel electrophoresis results. The first experiment describes the formation of direct strand breaks in double-stranded DNA induced by photoexcitation of the intercalated PF molecules. The second experiment demonstrates that the addition of the well-known electron acceptor, methylviologen, gives rise to a significant enhancement of the photochemical DNA strand cleavage effect. This occurs by an electron transfer step to methylviologen that renders the inital photoinduced charge separation between photoexcited PF and DNA irreversible. The third experiment demonstrates that the action spectrum of the DNA photocleavage matches the absorption spectrum of DNA-bound, intercalated PF molecules, which differs from that of free PF molecules. This result demonstrates that the photoinduced DNA strand cleavage is initiated by intercalated rather than free PF molecules.

Electrostatic self-assembly of exfoliated niobate nanosheets (Nb3O8-) and cobalt porphyrins (CoIIITMPyP) utilized for rapid construction of intercalated nanocomposite and exploration of electrocatalysis towards oxygen reduction

NASA Astrophysics Data System (ADS)

Xu, Jiasheng; Wang, Mengjun; Pan, Binbin; Li, Jinpeng; Xia, Bin; Zhang, Xiaobo; Tong, Zhiwei

To prepare the novel plate-like nanocomposite CoIIITMPyP/Nb3O8, the cationic cobalt (III) tetrakis-5, 10, 15, 20-(N-methyl-4-pyridyl) porphyrin (CoIIITMPyP) was intercalated into the interlayer of the perovskite structural material KNb3O8 via the electrostatic self-assembly of the positively charged CoIIITMPyP molecules and the electronegative Nb3O8- nanosheets. The Nb3O8- nanosheets was obtained by exfoliating the protonated product of niobate KNb3O8 in the tetrabutyl ammonium hydroxide (TBA+OH-) aqueous solution. The zeta potential was measured to indicate the stability and uniformity of the Nb3O8- nanosheet colloidal dispersion, and the structure and component of the parent material KNb3O8, the acidified product HNb3O8, and the interlayered nanocomposite CoIIITMPyP/Nb3O8 were characterized using XRD, FT-IR, SEM and AFM. Furthermore, the electrocatalytic activity toward the oxygen reduction reaction (ORR) of CoIIITMPyP/Nb3O8 hybrids modified GCE was investigated by the cyclic voltammetry (CV) measurements. The modified GCE exhibited good electrocatalytic activity toward ORR in consideration of the peak shift from -0.723V to -0.300V. The linear correlation of the reduction peak current and the square root of the scan rate suggested a diffusion controlled process.

Comment on "Flexible Asymmetric Supercapacitors Based on Nitrogen-Doped Graphene Hydrogels with Embedded Nickel Hydroxide Nanoplates".

PubMed

Vongehr, Sascha

2017-05-22

It is argued that the main claims of "Flexible Asymmetric Supercapacitors Based on Nitrogen-Doped Graphene Hydrogels with Embedded Nickel Hydroxide Nanoplates" are strongly exaggerated. By selecting first a subregion (ΔV) of the total voltage drop, the capacitance (C ΔV ) is inflated by 30 %. Then, by selecting different regions for different properties and using different ΔV values in different terms of a single expression for the energy density (E ΔV ), the value is doubled. A bending angle of only 45° is instead claimed to be 180°. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured pseudocapacitive materials decorated 3D graphene foam electrodes for next generation supercapacitors.

PubMed

Patil, Umakant; Lee, Su Chan; Kulkarni, Sachin; Sohn, Ji Soo; Nam, Min Sik; Han, Suhyun; Jun, Seong Chan

2015-04-28

Nowadays, advancement in performance of proficient multifarious electrode materials lies conclusively at the core of research concerning energy storage devices. To accomplish superior capacitance performance the requirements of high capacity, better cyclic stability and good rate capability can be expected from integration of electrochemical double layer capacitor based carbonaceous materials (high power density) and pseudocapacitive based metal hydroxides/oxides or conducting polymers (high energy density). The envisioned three dimensional (3D) graphene foams are predominantly advantageous to extend potential applicability by offering a large active surface area and a highly conductive continuous porous network for fast charge transfer with decoration of nanosized pseudocapacitive materials. In this article, we review the latest methodologies and performance evaluation for several 3D graphene based metal oxides/hydroxides and conducting polymer electrodes with improved electrochemical properties for next-generation supercapacitors. The most recent research advancements of our and other groups in the field of 3D graphene based electrode materials for supercapacitors are discussed. To assess the studied materials fully, a careful interpretation and rigorous scrutiny of their electrochemical characteristics is essential. Auspiciously, both nano-structuration as well as confinement of metal hydroxides/oxides and conducting polymers onto a conducting porous 3D graphene matrix play a great role in improving the performance of electrodes mainly due to: (i) active material access over large surface area with fast charge transportation; (ii) synergetic effect of electric double layer and pseudocapacitive based charge storing.

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Improved sensitivity via layered-double-hydroxide-uniformity-dependent chemiluminescence.

PubMed

Li, Zenghe; Wang, Dan; Yuan, Zhiqin; Lu, Chao

2016-12-01

In the last two decades nanoparticles have been widely applied to enhance chemiluminescence (CL). The morphology of nanoparticles has an important influence on nanoparticle-amplified CL. However, studies of nanoparticle-amplified CL focus mainly on the size and shape effects, and no attempt has been made to explore the influence of uniformity in nanoparticle-amplified CL processes. In this study we have investigated nanoparticle uniformity in the luminol-H 2 O 2 CL system using layered double hydroxides (LDHs) as a model material. The results demonstrated that the uniformity of LDHs played a key role in CL amplification. A possible mechanism is that LDHs with high uniformity possess abundant catalytic active sites, which results in high CL intensity. Meanwhile, the sensitivity for H 2 O 2 detection was increased by one order of magnitude (1.0 nM). Moreover, the uniform-LDH-amplified luminol CL could be applied to selective detection of glucose in human plasma samples. Furthermore, such a uniformity-dependent CL enhancement effect could adapted to other redox CL systems-for example, the peroxynitrous acid (ONOOH) CL system.

The use of dissolvable layered double hydroxide components in an in situ solid-phase extraction for chromatographic determination of tetracyclines in water and milk samples.

PubMed

Phiroonsoontorn, Nattaphorn; Sansuk, Sira; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

2017-10-13

This research presents a simple and green in situ solid phase extraction (is-SPE) combined with high-performance liquid chromatography (HPLC) for the simultaneous analysis of tetracyclines (TCs) including tetracycline, oxytetracycline, and chlortetracycline. In is-SPE, TCs were efficiently extracted through the precipitation formation of dissolvable layered double hydroxides (LDHs) by mixing the LDH components such as magnesium and aluminum ions (both in metal chloride salts) thoroughly in an alkaline sample solution. After the centrifugation, the precipitate was completely dissolved with trifluoroacetic acid to release the enriched TCs, and then analyzed by HPLC. Under optimized conditions, this method gave good enrichment factors (EFs) of 41-93 with low limits of detection (LODs) of 0.7-6μg/L and limits of quantitation (LOQs) of 3-15μg/L. Also, the proposed method was successfully applied for the determination of TCs in water and milk samples with the recoveries ranging from 81.7-108.1% for water and 55.7-88.7% for milk. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of the chloride ion as a hole scavenger on the photocatalytic conversion of CO2 in an aqueous solution over Ni-Al layered double hydroxides.

PubMed

Iguchi, Shoji; Teramura, Kentaro; Hosokawa, Saburo; Tanaka, Tsunehiro

2015-07-21

The photocatalytic conversion of CO2 into useful chemical compounds in water without using organic sacrificial reagents is a promising method to overcome environmental and energy problems. Various synthesized layered double hydroxides (LDHs) are capable of reducing CO2 to CO in an aqueous solution under UV light irradiation. However, it is difficult to oxidize H2O to O2 in a photocatalytic system using LDHs as photocatalysts. In this study, we investigated the photocatalytic conversion of CO2 using a Ni-Al LDH in an aqueous solution of NaCl. Hypochlorous acid (HClO) was produced as an oxidation product of Cl(-) with the formation of reduction products such as CO and H2 under photoirradiation. We propose the inclusion of Cl(-) in the reaction solution to be one of the most promising ways for obtaining a hole scavenger, an approach that would enable the construction of an artificial photosynthesis system for the conversion of CO2.

Electrodeposition to construct free-standing chitosan/layered double hydroxides hydro-membrane for electrically triggered protein release.

PubMed

Zhao, Pengkun; Zhao, Yanan; Xiao, Ling; Deng, Hongbing; Du, Yumin; Chen, Yun; Shi, Xiaowen

2017-10-01

In this study, we report the electrodeposition of a chitosan/layered double hydroxides (LDHs) hydro-membrane for protein release triggered by an electrical signal. The electrodeposition was performed in a chitosan and insulin loaded LDHs suspension in the absence of salt. A free-standing chitosan/LDHs hydro-membrane was generated on the electrode with improved mechanical properties, which is dramatically different from the weak hydrogel deposited in the presence of salt. The amount of LDHs in the hydro-membrane affects the optical transmittance and multilayered structure of the hybrid membrane. Compared to the weak chitosan/LDHs hydrogel, the hydro-membrane has a higher insulin loading capacity and the release of insulin is relatively slow. By biasing electrical potentials to the hydro-membrane, the release behavior of insulin can be adjusted accordingly. In addition, the chitosan/LDHs hydro-membrane showed no toxicity to cells. Our results provide a facile method to construct a chitosan/LDHs hybrid multilayered hydro-membrane and suggest the great potential of the hydro-membrane in controlled protein release. Copyright © 2017 Elsevier B.V. All rights reserved.

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

DOE PAGES

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga; ...

2016-03-09

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. In conclusion, the use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Chelator-Free Labeling of Layered Double Hydroxide Nanoparticles for in Vivo PET Imaging

NASA Astrophysics Data System (ADS)

Shi, Sixiang; Fliss, Brianne C.; Gu, Zi; Zhu, Yian; Hong, Hao; Valdovinos, Hector F.; Hernandez, Reinier; Goel, Shreya; Luo, Haiming; Chen, Feng; Barnhart, Todd E.; Nickles, Robert J.; Xu, Zhi Ping; Cai, Weibo

2015-11-01

Layered double hydroxide (LDH) nanomaterial has emerged as a novel delivery agent for biomedical applications due to its unique structure and properties. However, in vivo positron emission tomography (PET) imaging with LDH nanoparticles has not been achieved. The aim of this study is to explore chelator-free labeling of LDH nanoparticles with radioisotopes for in vivo PET imaging. Bivalent cation 64Cu2+ and trivalent cation 44Sc3+ were found to readily label LDH nanoparticles with excellent labeling efficiency and stability, whereas tetravalent cation 89Zr4+ could not label LDH since it does not fit into the LDH crystal structure. PET imaging shows that prominent tumor uptake was achieved in 4T1 breast cancer with 64Cu-LDH-BSA via passive targeting alone (7.7 ± 0.1%ID/g at 16 h post-injection; n = 3). These results support that LDH is a versatile platform that can be labeled with various bivalent and trivalent radiometals without comprising the native properties, highly desirable for PET image-guided drug delivery.

Effects of surface chemical properties of activated carbon modified by amino-fluorination for electric double-layer capacitor.

PubMed

Jung, Min-Jung; Jeong, Euigyung; Cho, Seho; Yeo, Sang Young; Lee, Young-Seak

2012-09-01

The surface of phenol-based activated carbon (AC) was seriatim amino-fluorinated with solution of ammonium hydroxide and hydrofluoric acid in varying ratio to fabricate electrode materials for use in an electric double-layer capacitor (EDLC). The specific capacitance of the amino-fluorinated AC-based EDLC was measured in a 1 M H(2)SO(4) electrolyte, in which it was observed that the specific capacitances increased from 215 to 389 Fg(-1) and 119 and 250 Fg(-1) with the current densities of 0.1 and 1.0 Ag(-1), respectively, in comparison with those of an untreated AC-based EDLC when the amino-fluorination was optimized via seriatim mixed solution of 7.43 mol L(-1) ammonium hydroxide and 2.06 mol L(-1) hydrofluoric acid. This enhancement of capacitance was attributed to the synergistic effects of an increased electrochemical activity due to the formation of surface N- and F-functional groups and increased, specific surface area, and mesopore volumes, all of which resulted from the amino-fluorination of the electrode material. Copyright © 2012 Elsevier Inc. All rights reserved.

Synthesis and optical properties of Mg-Al layered double hydroxides precursor powders

NASA Astrophysics Data System (ADS)

Lin, Chia-Hsuan; Chu, Hsueh-Liang; Hwang, Weng-Sing; Wang, Moo-Chin; Ko, Horng-Huey

2017-12-01

The synthesis and optical properties of Mg-Al layered double hydroxide (LDH) precursor powders were investigated using X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution TEM (HRTEM), UV-transmission spectrometer, and fluorescence spectrophotometer. The FT-IR results show that the intense absorption at around 1363-1377 cm-1 can be assigned to the antisymmetric ν3 mode of interlayer carbonate anions because the LDH phase contains some CO32-. The XRD results show that all of the Mg-Al LDH precursor powders contain only a single phase of [Mg0.833Al0.167(OH)2](CO3)0.083.(H2O)0.75 but have broad and weak intensities of peaks. All of Mg-Al LDHs precursor powders before calcination have the same photoluminescence (PL) spectra. Moreover, these spectra were excited at λex = 235 nm, and the broad emission band was in the range 325-650 nm. In the range, there were relatively strong intensity at around 360, 407 and 510 nm, respectively.

Gadolinium-Doped Gallic Acid-Zinc/Aluminium-Layered Double Hydroxide/Gold Theranostic Nanoparticles for a Bimodal Magnetic Resonance Imaging and Drug Delivery System.

PubMed

Sani Usman, Muhammad; Hussein, Mohd Zobir; Fakurazi, Sharida; Masarudin, Mas Jaffri; Ahmad Saad, Fathinul Fikri

2017-08-31

We have developed gadolinium-based theranostic nanoparticles for co-delivery of drug and magnetic resonance imaging (MRI) contrast agent using Zn/Al-layered double hydroxide as the nanocarrier platform, a naturally occurring phenolic compound, gallic acid (GA) as therapeutic agent, and Gd(NO₃)₃ as diagnostic agent. Gold nanoparticles (AuNPs) were grown on the system to support the contrast for MRI imaging. The nanoparticles were characterized using techniques such as Hi-TEM, XRD, ICP-ES. Kinetic release study of the GA from the nanoparticles showed about 70% of GA was released over a period of 72 h. The in vitro cell viability test for the nanoparticles showed relatively low toxicity to human cell lines (3T3) and improved toxicity on cancerous cell lines (HepG2). A preliminary contrast property test of the nanoparticles, tested on a 3 Tesla MRI machine at various concentrations of GAGZAu and water (as a reference) indicates that the nanoparticles have a promising dual diagnostic and therapeutic features to further develop a better future for clinical remedy for cancer treatment.

Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

NASA Astrophysics Data System (ADS)

Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

2017-02-01

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

Facile synthesis of three dimensional hierarchical Co-Al layered double hydroxides on graphene as high-performance materials for supercapacitor electrode.

PubMed

Hao, Jinhui; Yang, Wenshu; Zhang, Zhe; Lu, Baoping; Ke, Xi; Zhang, Bailin; Tang, Jilin

2014-07-15

A facile simple hydrothermal method combined with a post-solution reaction is developed to grow interconnected three dimensional (3D) hierarchical Co-Al layered double hydroxides (LDHs) on reduced graphene oxide (rGO). The obtained 3D hierarchical rGO-LDHs are characterized by field emission scanning electron microscopy, X-ray diffraction, and X-ray photo-electron spectroscopy. As LDHs nanosheets directly grow on the surface of rGO via chemical covalent bonding, the rGO could provide facile electron transport paths in the electrode for the fast Faradaic reaction. Moreover, benefiting from the rational 3D hierarchical structural, the rGO-LDHs demonstrate excellent electrochemical properties with a combination of high charge storage capacitance, fast rate capability and stable cycling performance. Remarkably, the 3D hierarchical rGO-LDHs exhibit specific capacitance values of 599 F g(-1) at a constant current density of 4 A g(-1). The rGO-LDHs also show high charge-discharge reversibility with an efficiency of 92.4% after 5000 cycles. Copyright © 2014 Elsevier Inc. All rights reserved.

Synthesis of NiMn-LDH Nanosheet@Ni3S2 Nanorod Hybrid Structures for Supercapacitor Electrode Materials with Ultrahigh Specific Capacitance.

PubMed

Yu, Shuai; Zhang, Yingxi; Lou, Gaobo; Wu, Yatao; Zhu, Xinqiang; Chen, Hao; Shen, Zhehong; Fu, Shenyuan; Bao, Binfu; Wu, Limin

2018-03-27

One of the key challenges for pseudocapacitive electrode materials with highly effective capacitance output and future practical applications is how to rationally construct hierarchical and ordered hybrid nanoarchitecture through the simple process. Herein, we design and synthesize a novel NiMn-layered double hydroxide nanosheet@Ni 3 S 2 nanorod hybrid array supported on porous nickel foam via a one-pot hydrothermal method. Benefited from the ultrathin and rough nature, the well-defined porous structure of the hybrid array, as well as the synergetic effect between NiMn-layered double hydroxide nanosheets and Ni 3 S 2 nanorods, the as-fabricated hybrid array-based electrode exhibits an ultrahigh specific capacitance of 2703 F g -1 at 3 A g -1 . Moreover, the asymmetric supercapacitor with this hybrid array as a positive electrode and wood-derived activated carbon as a negative electrode demonstrates high energy density (57 Wh Kg -1 at 738 W Kg -1 ) and very good electrochemical cycling stability.

Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga

2016-05-01

The hydrogenation of furfural is investigated over various reduced nickel mixed metal oxides derived from layered double hydroxides (LDHs) containing Ni-Mg-Al and Ni-Co-Al. Upon reduction, relatively large Ni(0) domains develop in the Ni-Mg-Al catalysts, whereas in the Ni-Co-Al catalysts smaller metal particles of Ni(0) and Co(0), potentially as alloys, are formed, as evidenced by XAS, XPS, STEM and EELS. All the reduced Ni catalysts display similar selectivities towards major hydrogenation products (furfuryl alcohol and tetrahydrofurfuryl alcohol), though the side products varied with the catalyst composition. The 1.1Ni-0.8Co-Al catalyst showed the greatest activity per titrated site when compared to the othermore » catalysts, with promising activity compared to related catalysts in the literature. The use of base metal catalysts for hydrogenation of furanic compounds may be a promising alternative to the well-studied precious metal catalysts for making biomass-derived chemicals if catalyst selectivity can be improved in future work by alloying or tuning metal-oxide support interactions.« less

Universal biomimetic preparation and immobilization of layered double hydroxide films and adsorption behavior

NASA Astrophysics Data System (ADS)

Zhou, Wei; Zhang, Wenpeng; Chen, Zilin

2017-01-01

Preparation and immobilization of layered double hydroxides (LDHs) film onto multiple substrates is important and challenging in functional materials fields by date. In this work, a simple and universal polydopamine (PD)-based layer-by-layer assembly strategy was developed for the immobilization of LDHs film onto surfaces such as polypropylene chip, glass slides and metal coins. The surface of substrates was firstly modified by polydopamine functionalization, and then LDHs film was synthesized via urea method and directly immobilized on the PD layer by in situ growing strategy in one step. The PD layer as well as the final LDHs film was characterized by energy dispersive X-ray spectroscopy, scanning electron microscope, infrared spectroscopy, X-ray diffraction pattern and X-ray photoelectron spectra. It has been demonstrated the formation of the dense and homogeneous nanoscaled LDHs film with 400 nm thickness. Adsorption behavior of the fabricated NiAl-LDHs film toward anionic dyes and pharmaceuticals was further assessed. To demonstrate their extensive application, fast and high efficient adsorption of anionic dyes and pharmaceuticals was achieved by NiAl-LDHs-modified polypropylene centrifugal tube.

Crosslinking to enhance colloidal stability and redispersity of layered double hydroxide nanoparticles.

PubMed

Zuo, Huali; Gu, Zi; Cooper, Helen; Xu, Zhi Ping

2015-12-01

This article introduces a strategy for stabilizing and redispersing layered double hydroxide (LDH) nanoparticles by crosslinking bovine serum albumin (BSA) coated onto the surface. The strategy involves optimization of the amount of the crosslinking agent glutaraldehyde (GTA) to achieve minimal aggregation and ready redispersion. LDH nanoparticles were prepared by co-precipitation and hydrothermal treatment, with subsequent BSA coating at the BSA/LDH mass ratio of 5:2. BSA coated onto LDH nanoparticles was crosslinked with different amounts of GTA. Aggregation studies using dilution assays, dynamic light scattering, and zeta potential analysis indicated that severe aggregation at lower LDH nanoparticle concentrations can be prevented by proper crosslinking of BSA with GTA. The GTA-crosslinked BSA-coated nanoparticles showed excellent redispersity compared to the non-crosslinked nanoparticles. In vitro cytotoxicity and cell uptake were found to be minimally affected by GTA-crosslinking. The new strategy therefore provides a much more effective method for the prevention of LDH nanoparticle aggregation and improved LDH nanoparticle redispersion for use in a wide variety of bio-applications in vitro and in vivo. Copyright © 2015 Elsevier Inc. All rights reserved.

Regulating the local pH level of titanium via Mg-Fe layered double hydroxides films for enhanced osteogenesis.

PubMed

Li, Qianwen; Wang, Donghui; Qiu, Jiajun; Peng, Feng; Liu, Xuanyong

2018-05-01

Hard tissue implant materials which can cause a suitable alkaline microenvironment are thought to be beneficial for stimulating osteoblast differentiation while suppressing osteoclast generation. To make the local pH around the interface between materials and cells controllable, we prepared a series of Mg-Fe layered double hydroxide (LDH) films on acid-etched pure titanium surfaces via hydrothermal treatment. By adjusting the Mg/Fe proportion ratio, the interlayer spacing of Mg-Fe LDHs was regulated, making their OH- exchange abilities adjustable, and this ultimately resulted in a microenvironment with a controllable pH value. In vitro experiments demonstrated that the Mg-Fe LDH film-modified titanium surface possessed good biocompatibility and osteogenic activity, especially the Mg-Fe LDH film with Mg/Fe proportion ratio of 4, which could form a suitable alkaline microenvironment for the growth and osteogenetic differentiation of stem cells. These results demonstrate the potential application of the prepared Mg-Fe LDH films in enhancing the osteogenesis of implant materials while providing a new way into the design of controllable alkaline environment.

Synthesis of Fluorinated Graphene/CoAl-Layered Double Hydroxide Composites as Electrode Materials for Supercapacitors.

PubMed

Peng, Weijun; Li, Hongqiang; Song, Shaoxian

2017-02-15

CoAl-layered double hydroxide/fluorinated graphene (CoAl-LDH/FGN) composites were fabricated via a two-step hydrothermal method. The synthesized CoAl-LDH/FGN composites have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and electrochemical measurements. The results indicated that the fluorinated carbon with various configuration forms were grafted onto the framework of graphene, and the C-F bond configuration and fluorine content could be tuned by the fluorination time. Most of semi-ionic C-F bonds were formed at an appropriate fluorination time and, then, converted into fluorine rich surface groups (such as CF 2 , CF 3 , etc.) which were electrochemically inactive as the fluorination time prolonged. Moreover, the CoAl-LDH/FGN composites prepared at the optimal fluorination time exhibited the highest specific capacitance (1222 F/g at 1 A/g), the best rate capability, and the most stable capacitance retention, which offered great promise as electrode materials for supercapacitors.

Acid Green 1 removal from wastewater by layered double hydroxides

NASA Astrophysics Data System (ADS)

Elkhattabi, El Hassan; Lakraimi, Mohamed; Berraho, Moha; Legrouri, Ahmed; Hammal, Radouan; El Gaini, Layla

2018-03-01

The paper presents the removal of Acid Green 1 (AG1) from aqueous solutions by [Zn-Al-Cl]-layered double hydroxides (LDHs). The LDH was prepared by coprecipitation at constant pH. The affinity of this material for AG1 was studied as a function of contact time, pH of the solution, LDH dose and AG1/LDH mass ratio. It was found that 32 h are enough to reach the equilibrium with a maximum retention at pH 8 for an LDH dose of 100 mg and with an AG1/LDH mass ratio higher than 2. The adsorption isotherm is of L-type, as described by the Langmuir model. The results demonstrate that AG1 retention on LDHs occurs by adsorption on external surface when AG1/LDH mass ratio is equal or lower than 2 and by both adsorption and interlayer ion exchange for ratios higher than 2. A mechanism for the AG1 removal has been confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric-differential thermal analyses and scanning electron microscopy.

Layered Double Hydroxide Nanotransporter for Molecule Delivery to Intact Plant Cells

PubMed Central

Bao, Wenlong; Wang, Junya; Wang, Qiang; O’Hare, Dermot; Wan, Yinglang

2016-01-01

Here we report a powerful method that facilitates the transport of biologically active materials across the cell wall barrier in plant cells. Positively charged delaminated layered double hydroxide lactate nanosheets (LDH-lactate-NS) with a 0.5‒2 nm thickness and 30‒60 nm diameter exhibit a high adsorptive capacity for negatively charged biomolecules, including fluorescent dyes such as tetramethyl rhodamine isothiocyanate (TRITC), fluorescein isothiocyanate isomer I(FITC) and DNA molecules, forming neutral LDH-nanosheet conjugates. These neutral conjugates can shuttle the bound fluorescent dye into the cytosol of intact plant cell very efficiently. Furthermore, typical inhibitors of endocytosis and low temperature incubation did not prevent LDH-lactate-NS internalization, suggesting that LDH-lactate-NS penetrated the plasma membrane via non-endocytic pathways, which will widen the applicability to a variety of plant cells. Moreover, the absence of unwanted side effects in our cytological studies, and the nuclear localization of ssDNA-FITC suggest that nano-LDHs have potential application as a novel gene carrier to plants. PMID:27221055

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

NASA Technical Reports Server (NTRS)

Pitsch, S.; Krishnamurthy, R.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

2000-01-01

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

LDHs/graphene film on aluminum alloys for active protection

NASA Astrophysics Data System (ADS)

Zhang, You; Yu, Peihang; Wang, Juping; Li, Yingdong; Chen, Fei; Wei, Kai; Zuo, You

2018-03-01

A layered double hydroxides (LDHs) nanocontainer film modified with graphene was fabricated on aluminum alloy via a facile two-step process. The structure, morphology and composition of LDHs/graphene film were investigated. Graphene layers were able to seal the pores of nest-like LDHs film. After the modification of graphene, the LDHs film presented hydrophobic (CA 127.8°) and enhanced anticorrosion properties. The active anticorrosion property of the composite film was attributed to the double functions of the impermeable and inert graphene layer and the active inhibitor-loaded LDHs underling film.

Intrinsically Labeled Fluorescent Oligonucleotide Probes on Quantum Dots for Transduction of Nucleic Acid Hybridization.

PubMed

Shahmuradyan, Anna; Krull, Ulrich J

2016-03-15

Quantum dots (QDs) have been widely used in chemical and biosensing due to their unique photoelectrical properties and are well suited as donors in fluorescence resonance energy transfer (FRET). Selective hybridization interactions of oligonucleotides on QDs have been determined by FRET. Typically, the QD-FRET constructs have made use of labeled targets or have implemented labeled sandwich format assays to introduce dyes in proximity to the QDs for the FRET process. The intention of this new work is to explore a method to incorporate the acceptor dye into the probe molecule. Thiazole orange (TO) derivatives are fluorescent intercalating dyes that have been used for detection of double-stranded nucleic acids. One such dye system has been reported in which single-stranded oligonucleotide probes were doubly labeled with adjacent thiazole orange derivatives. In the absence of the fully complementary (FC) oligonucleotide target, the dyes form an H-aggregate, which results in quenching of fluorescence emission due to excitonic interactions between the dyes. The hybridization of the FC target to the probe provides for dissociation of the aggregate as the dyes intercalate into the double stranded duplex, resulting in increased fluorescence. This work reports investigation of the dependence of the ratiometric signal on the type of linkage used to conjugate the dyes to the probe, the location of the dye along the length of the probe, and the distance between adjacent dye molecules. The limit of detection for 34mer and 90mer targets was found to be identical and was 10 nM (2 pmol), similar to analogous QD-FRET using labeled oligonucleotide target. The detection system could discriminate a one base pair mismatch (1BPM) target and was functional without substantial compromise of the signal in 75% serum. The 1BPM was found to reduce background signal, indicating that the structure of the mismatch affected the environment of the intercalating dyes.

Structure of oxides prepared by decomposition of layered double Mg–Al and Ni–Al hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherepanova, Svetlana V.; Novosibirsk State University, Novosibirsk; Leont’eva, Natalya N., E-mail: n_n_leonteva@list.ru

2015-05-15

Abstracts: Thermal decomposition of Mg–Al and Ni–Al layered double hydroxides LDH at temperatures lower than 800 °C leads to the formation of oxides with different structures. Mg–Al oxide has a very defective structure and consists of octahedral layers as in periclase MgO and mixed octahedral–tetrahedral layers as in spinel MgAl{sub 2}O{sub 4}. Mixed Ni–Al oxide has a sandwich-like structure, consisting of a core with Al-doped NiO-like structure and some surface layers with spinel NiAl{sub 2}O{sub 4} structure epitaxial connected with the core. Suggested models were verified by simulation of X-ray diffraction patterns using DIFFaX code, as well as HRTEM, IR-,more » UV-spectroscopies, and XPS. - Graphical abstract: In the Mg–Al layered double hydroxide Al{sup 3+} ions migrate into interlayers during decomposition. The Mg–Al oxide represents sequence of octahedral and octahedral–tetrahedral spinel layers with vacancies. The Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers as a result of migration of Al{sup 3+} ions on the surface. The models explain the presence and absence of “memory effect” for the Mg–Al and Ni–Al oxides, respectively. - Highlights: • We study products of Mg(Ni)–Al LDH decomposition by calcination at 500(400)–800 °C. • In Mg–Al/Ni–Al LDH Al ions migrate into interlayers/on the surface during decomposition. • Mg–Al oxide represents sequence of periclase- and spinel-like layers with vacancies. • Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers. • The models explain the presence/absence of “memory effect” for Mg–Al/Ni–Al oxides.« less

Graphene-based materials via benzidine-assisted exfoliation and reduction of graphite oxide and their electrochemical properties

NASA Astrophysics Data System (ADS)

Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Boukos, N.; Psycharis, V.; Lei, C.; Lekakou, C.; Petridis, D.; Trapalis, C.

2017-01-01

Benzidine, a compound bearing aromatic rings and terminal amino groups, was employed for the intercalation and simultaneous reduction of graphite oxide (GO). The aromatic diamine can be intercalated into GO as follows: (1) by grafting with the epoxy groups of GO, (2) by hydrogen bonding with the oxygen containing groups of GO. Stacking between benzidine aromatic rings and unoxidized domains of GO may occur through π-π interaction. The role of benzidine is influenced by pH conditions and the weight ratio GO/benzidine. Two weight ratios were tested i.e. 1:2 and 1:3. Under strong alkaline conditions through K2CO3 addition (pH ∼10.4-10.6) both intercalation and reduction of GO via amino groups occur, while under strong acidic conditions through HCl addition (pH ∼1.4-2.2) π-π stacking is preferred. When no base or acid is added (pH ∼5.2) and the weight ratio is 1:2, there are indications that reduction and π-π stacking occur, while at a GO/benzidine weight ratio 1:3 intercalation via amino groups and reduction seem to dominate. The aforementioned remarks render benzidine a multifunctional tool towards production of reduced graphene oxide. The effect of pH conditions and the GO/benzidine weight ratio on the quality and the electrochemical properties of the produced graphene-based materials were investigated. Cyclic voltammetry measurements using three-electrode cell and KCl aqueous solution as an electrolyte gave specific capacitance values up to ∼178 F/g. When electric double-layer capacitors (EDLC) were fabricated from these materials, the maximum capacitance in organic electrolyte i.e., tetraethyl ammonium tetrafluoroborate (TEABF4) in polycarbonate (PC) was ∼29 F/g.

Ion chromatographic determination of hydroxide ion on monolithic reversed-phase silica gel columns coated with nonionic and cationic surfactants.

PubMed

Xu, Qun; Mori, Masanobu; Tanaka, Kazuhiko; Ikedo, Mikaru; Hu, Wenzhi; Haddad, Paul R

2004-07-02

The determination of hydroxide by ion chromatography (IC) is demonstrated using a monolithic octadecylsilyl (ODS)-silica gel column coated first with a nonionic surfactant (polyoxyethylene (POE)) and then with a cationic surfactant (cetyltrimethylammonium bromide (CTAB)). This stationary phase, when used in conjunction with a 10 mmol/l sodium sulfate eluent at pH 8.2, was found to be suitable for the rapid and efficient separation of hydroxide from some other anions, based on a conventional ion-exchange mechanism. The peak directions and detection responses for these ions were in agreement with their known limiting equivalent ionic conductance values. Under these conditions, a linear calibration plot was obtained for hydroxide ion over the range 16 micromol/l to 15 mmol/l, and the detection limit determined at a signal-to-noise ratio of 3 was 6.4 micromol/l. The double-coated stationary phase described above was shown to be superior to a single coating of cetyltrimethylammonium bromide alone, in terms of separation efficiency and stability of the stationary phase. A range of samples comprising solutions of some strong and weak bases was analyzed by the proposed method and the results obtained were in good agreement with those obtained by conventional potentiometric pH measurement.

Interaction of thionine with triple-, double-, and single-stranded RNAs.

PubMed

Lozano, Héctor J; García, Begoña; Busto, Natalia; Leal, José M

2013-01-10

The interaction of thionine with triple, double, and single RNA helices has been fully characterized by thermodynamic and kinetic methods. The nature of the interaction of thionine with the synthetic polynucleotides poly(rU), poly(rA)·poly(rU), and poly(rA)·2poly(rU) has been studied at pH = 7.0 and 25 °C by UV absorbance, fluorescence, circular dichroism spectroscopy, viscometry, differential scanning calorimetry, and T-jump kinetic measurements. The results show that at I = 0.1 M thionine binds to a single poly(rU) strand, destabilizes the poly(rA)·2poly(rU) triplex by external binding, and intercalates into poly(rA)·poly(rU) with similar affinity to the thionine/DNA intercalated complex (Paul, P.; Kumar, G. S. J. Fluoresc. 2012, 22, 71-80). On the other hand, the differential scanning calorimetry measurements performed with thionine display a point in which the heat capacity remains unaltered, revealing the equilibrium of isothermal denaturation: thionine/poly(rA)·2poly(rU) + thionine ⇌ thionine/poly(rA)·poly(rU) + thionine/poly(rU), an outcome supported by the other techniques used. The denaturation equilibrium constant, K(D) (25 °C) = 522 M(-1), was evaluated from the affinity with the single, duplex, and triplex RNA.

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda).

PubMed

Seng, Hoi-Ling; Ong, Han-Kiat Alan; Rahman, Raja Noor Zaliha Raja Abd; Yamin, Bohari M; Tiekink, Edward R T; Tan, Kong Wai; Maah, Mohd Jamil; Caracelli, Ignez; Ng, Chew Hee

2008-11-01

The binding selectivity of the M(phen)(edda) (M=Cu, Co, Ni, Zn; phen=1,10-phenanthroline, edda=ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(II) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N(4)O(2) octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling.

Human telomeric DNA: G-quadruplex, i-motif and Watson–Crick double helix

PubMed Central

Phan, Anh Tuân; Mergny, Jean-Louis

2002-01-01

Human telomeric DNA composed of (TTAGGG/CCCTAA)n repeats may form a classical Watson–Crick double helix. Each individual strand is also prone to quadruplex formation: the G-rich strand may adopt a G-quadruplex conformation involving G-quartets whereas the C-rich strand may fold into an i-motif based on intercalated C·C+ base pairs. Using an equimolar mixture of the telomeric oligonucleotides d[AGGG(TTAGGG)3] and d[(CCCTAA)3CCCT], we defined which structures existed and which would be the predominant species under a variety of experimental conditions. Under near-physiological conditions of pH, temperature and salt concentration, telomeric DNA was predominantly in a double-helix form. However, at lower pH values or higher temperatures, the G-quadruplex and/or the i-motif efficiently competed with the duplex. We also present kinetic and thermodynamic data for duplex association and for G-quadruplex/i-motif unfolding. PMID:12409451

Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

PubMed Central

Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

2016-01-01

Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as −0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at −0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under −0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination. PMID:27487918

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

PubMed

Li, Wei; Livi, Kenneth J T; Xu, Wenqian; Siebecker, Matthew G; Wang, Yujun; Phillips, Brian L; Sparks, Donald L

2012-11-06

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Single Fluorescence Channel-based Multiplex Detection of Avian Influenza Virus by Quantitative PCR with Intercalating Dye

PubMed Central

Ahberg, Christian D.; Manz, Andreas; Neuzil, Pavel

2015-01-01

Since its invention in 1985 the polymerase chain reaction (PCR) has become a well-established method for amplification and detection of segments of double-stranded DNA. Incorporation of fluorogenic probe or DNA intercalating dyes (such as SYBR Green) into the PCR mixture allowed real-time reaction monitoring and extraction of quantitative information (qPCR). Probes with different excitation spectra enable multiplex qPCR of several DNA segments using multi-channel optical detection systems. Here we show multiplex qPCR using an economical EvaGreen-based system with single optical channel detection. Previously reported non quantitative multiplex real-time PCR techniques based on intercalating dyes were conducted once the PCR is completed by performing melting curve analysis (MCA). The technique presented in this paper is both qualitative and quantitative as it provides information about the presence of multiple DNA strands as well as the number of starting copies in the tested sample. Besides important internal control, multiplex qPCR also allows detecting concentrations of more than one DNA strand within the same sample. Detection of the avian influenza virus H7N9 by PCR is a well established method. Multiplex qPCR greatly enhances its specificity as it is capable of distinguishing both haemagglutinin (HA) and neuraminidase (NA) genes as well as their ratio. PMID:26088868

Interactions of vitamin K3 with herring-sperm DNA using spectroscopy and electrochemistry.

PubMed

Huang, Jianhang; Wang, Xingming; Fei, Dan; Ding, Lisheng

2010-10-01

By means of ultraviolet-visible (UV-Vis) and fluorescence spectra, the binding ratio between vitamin K(3) and herring-sperm DNA in a physiological pH environment (pH = 7.40) was determined as n(K3):n(DNA) = 2:1, and the binding constants of vitamin K(3) binding to DNA at different temperatures were determined as K(θ)(298K) = 1.28 × 10(5) L·mol(-1) and K(θ)(310K) = 7.19 × 10(4) L·mol(-1), which were confirmed using the double reciprocal method are Δ(r)H(m)(θ) = -3.57 × 10(4) J·mol(-1), Δ(r)G(m)(θ) = -2.92 × 10(4) J·mol(-1), and Δ(r)S(m)(θ) = 217.67 J·mol(-1)K(-1). The driving power of this process was enthalpy. An intercalation binding of the vitamin K(3) with DNA was supported by a competitive experiment using acridine orange (AO) as a spectral probe. By combination analysis of the Scatchard method and cyclic voltammetry, we suggested that the interaction mode between vitamin K(3) and herring-sperm DNA would be a mixed mode. The quinonoid, duality fused-ring of vitamin K(3) can intercalate into the base pairs of DNA, and there is an electrostatic binding along with intercalation binding.

Electrochemical Transport Phenomena in Hybrid Pseudocapacitors under Galvanostatic Cycling

DOE PAGES

d'Entremont, Anna L.; Girard, Henri -Louis; Wang, Hainan; ...

2015-11-18

Here, this study aims to provide insights into the electrochemical transport and interfacial phenomena in hybrid pseudocapacitors under galvanostatic cycling. Pseudocapacitors are promising electrical energy storage devices for applications requiring large power density. They also involve complex, coupled, and multiscale physical phenomena that are difficult to probe experimentally. The present study performed detailed numerical simulations for a hybrid pseudocapacitor with planar electrodes and binary, asymmetric electrolyte under various cycling conditions, based on a first-principles continuum model accounting simultaneously for charge storage by electric double layer (EDL) formation and by faradaic reactions with intercalation. Two asymptotic regimes were identified corresponding tomore » (i) dominant faradaic charge storage at low current and low frequency or (ii) dominant EDL charge storage at high current and high frequency. Analytical expressions for the intercalated ion concentration and surface overpotential were derived for both asymptotic regimes. Features of typical experimentally measured cell potential were physically interpreted. These insights could guide the optimization of hybrid pseudocapacitors.« less

NMR solution structure of an N2-guanine DNA adduct derived from the potent tumorigen dibenzo[a,l]pyrene: Intercalation from the minor groove with ruptured Watson-Crick base pairing

PubMed Central

Tang, Yijin; Liu, Zhi; Ding, Shuang; Lin, Chin H.; Cai, Yuqin; Rodriguez, Fabian A.; Sayer, Jane M.; Jerina, Donald M.; Amin, Shantu; Broyde, Suse; Geacintov, Nicholas E.

2012-01-01

The most potent tumorigen identified among the polycyclic aromatic hydrocarbons (PAH) is the non-planar fjord region dibenzo[a,l]pyrene (DB[a,l]P). It is metabolically activated in vivo through the widely-studied diol epoxide (DE) pathway to form covalent adducts with DNA bases, predominantly guanine and adenine. The (+)-11S,12R,13R,14S DE enantiomer forms adducts via its C14-position with the exocyclic amino group of guanine. Here, we present the first NMR solution structure of a DB[a,l]P-derived adduct, the 14R (+)-trans-anti-DB[a,l]P–N2-dG (DB[a,l]P-dG) lesion in double-stranded DNA. In contrast to the stereochemically identical benzo[a]pyrene-derived N2-dG adduct (B[a]P-dG) in which the B[a]P rings reside in the B-DNA minor groove on the 3’-side of the modifed deoxyguanosine, in the DB[a,l]P-derived adduct the DB[a,l]P rings intercalate into the duplex on the 3’-side of the modified base from the sterically crowded minor groove. Watson-Crick base pairing of the modified guanine with the partner cytosine is broken, but these bases retain some stacking with the bulky DB[a,l]P ring system. This new theme in PAH DE - DNA adduct conformation differs from: (1) the classical intercalation motif where Watson-Crick base-pairing is intact at the lesion site, and (2) the base-displaced intercalation motif in which the damaged base and its partner are extruded from the helix . The structural considerations that lead to the intercalated conformation of the DB[a,l]P-dG lesion in contrast to the minor groove alignment of the B[a]P-dG adduct, and the implications of the DB[a,l]P-dG conformational motif for the recognition of such DNA lesions by the human nucleotide excision repair apparatus, are discussed. PMID:23121427

Nuclear magnetic resonance solution structure of an N(2)-guanine DNA adduct derived from the potent tumorigen dibenzo[a,l]pyrene: intercalation from the minor groove with ruptured Watson-Crick base pairing.

PubMed

Tang, Yijin; Liu, Zhi; Ding, Shuang; Lin, Chin H; Cai, Yuqin; Rodriguez, Fabian A; Sayer, Jane M; Jerina, Donald M; Amin, Shantu; Broyde, Suse; Geacintov, Nicholas E

2012-12-04

The most potent tumorigen identified among the polycyclic aromatic hydrocarbons (PAH) is the nonplanar fjord region dibenzo[a,l]pyrene (DB[a,l]P). It is metabolically activated in vivo through the widely studied diol epoxide (DE) pathway to form covalent adducts with DNA bases, predominantly guanine and adenine. The (+)-11S,12R,13R,14S DE enantiomer forms adducts via its C14 position with the exocyclic amino group of guanine. Here, we present the first nuclear magnetic resonance solution structure of a DB[a,l]P-derived adduct, the 14R-(+)-trans-anti-DB[a,l]P-N(2)-dG (DB[a,l]P-dG) lesion in double-stranded DNA. In contrast to the stereochemically identical benzo[a]pyrene-derived N(2)-dG adduct (B[a]P-dG) in which the B[a]P rings reside in the B-DNA minor groove on the 3'-side of the modifed deoxyguanosine, in the DB[a,l]P-derived adduct the DB[a,l]P rings intercalate into the duplex on the 3'-side of the modified base from the sterically crowded minor groove. Watson-Crick base pairing of the modified guanine with the partner cytosine is broken, but these bases retain some stacking with the bulky DB[a,l]P ring system. This new theme in PAH DE-DNA adduct conformation differs from (1) the classical intercalation motif in which Watson-Crick base pairing is intact at the lesion site and (2) the base-displaced intercalation motif in which the damaged base and its partner are extruded from the helix. The structural considerations that lead to the intercalated conformation of the DB[a,l]P-dG lesion in contrast to the minor groove alignment of the B[a]P-dG adduct, and the implications of the DB[a,l]P-dG conformational motif for the recognition of such DNA lesions by the human nucleotide excision repair apparatus, are discussed.

The influence of oxalate-promoted growth of saponite and talc crystals

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2013-01-01

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

DNA sensing by a Eu-binding peptide containing a proflavine unit.

PubMed

Ancel, Laetitia; Gateau, Christelle; Lebrun, Colette; Delangle, Pascale

2013-01-18

Synthesis of a lanthanide-binding peptide (LBP) for the detection of double-stranded DNA is presented. A proflavine moiety was introduced into a high affinity LBP involving two unnatural chelating amino acids in the Ln ion coordination. The Eu(3+)-LBP complex is demonstrated to bind to ct-DNA and to sensitize Eu luminescence. The DNA binding process is effectively detected via the Eu-centered luminescence thanks to the intimate coupling between the LBP scaffold and DNA intercalating unit.

EFFECTS OF MAGNESIUM PEMOLINE UPON HUMAN LEARNING, MEMORY, AND PERFORMANCE TESTS.

ERIC Educational Resources Information Center

SMITH, RONALD G.

THIS STUDY WAS CONDUCTED DURING 1966 TO DETERMINE THE EFFECTS OF MAGNESIUM PEMOLINE (A COMBINATION OF 2-IMINO-5-PHENYL-4-OXAZOLIDINONE AND MAGNESIUM HYDROXIDE) ON A VARIETY OF HUMAN LEARNING, MEMORY, AND PERFORMANCE TASKS. MAGNESIUM PEMOLINE (25 OR 37.5 MG) OR A PLACEBO WAS ADMINISTERED ORALLY ON A DOUBLE-BLIND BASIS TO INTELLIGENCE-MATCHED GROUPS…

The Synthesis and Characterization of Rouaite, a Copper Hydroxy Nitrate: An Integrated First-Year Laboratory Project

ERIC Educational Resources Information Center

Bushong, Elizabeth J.; Yoder, Claude H.

2009-01-01

The synthesis and analysis of a copper hydroxy nitrate provides an exposure to a simple ionic synthesis, qualitative analysis of copper and nitrate, two gravimetric analyses (copper and nitrate), one volumetric analysis (hydroxide), and a colorimetric analysis (copper). The results allow the student to determine the identity of the double salt and…

Ultrasonically assisted solvothermal synthesis of novel Ni/Al layered double hydroxide for capturing of Cd(II) from contaminated water

NASA Astrophysics Data System (ADS)

Rahmanian, Omid; Maleki, Mohammad Hassan; Dinari, Mohammad

2017-11-01

A novel adsorbent of nickel aluminum layered double hydroxide (Ni/Al-LDH) was prepared through the precipitation of metal nitrates by ultrasonically assisted solvothermal method. The surface morphology, chemical structure and thermal properties of this compound were examined by X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) techniques. The XRD, TEM and FE-SEM results established that the synthesized LDH have a well-ordered layer structure with good crystalline nature. Then it was applied to remove excessive Cd(II) ions from water and the effects of contact time, pH and adsorbent dose were examined at initial Cd(II) concentration of 10 mg/L. Results show that the time required to reach equilibrium was fast (40 min) and working pH solution was neutral (pH 7). Langmuir and Freundlich model of adsorption isotherms were explored; the results show that the Freundlich model was better fitted than that Langmuir model. This results predicting a multilayer adsorption of Cd(II) on LDH. The equilibrium kinetic adsorption data were fixed to the pseudo-second order kinetic equation.

Mechano-hydrothermal preparation of Li-Al-OH layered double hydroxides

NASA Astrophysics Data System (ADS)

Zhang, Fengrong; Hou, Wanguo

2018-05-01

A mechano-hydrothermal (MHT) method was used to synthesize Li-Al-OH layered double hydroxides (LDHs) from LiOH·H2O, Al(OH)3 and H2O as starting materials. A two-step synthesis was conducted, that is, Al(OH)3 was milled for 1 h, followed by hydrothermal treatment with LiOH·H2O solution. Effects of the LiOH/Al(OH)3 molar ratio (RLi/Al) and hydrothermal temperature (Tht) on the crystallinity, morphology, and composition of the product were examined. The resulting LDHs were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, Fourier transform infrared, and elemental analyses. The results showed that pre-milling plays a key role in the LDH formation during subsequent hydrothermal treatment. The Li/Al molar ratio of the obtained LDHs keeps constant at 0.5, independent from theRLi/Al (0.5-5.0) in the starting materials. An increase in the Tht (20-80 °C) can enhance the crystallinity and morphology regularity of the products. The so-obtained Li-Al-OH LDHs exhibit high crystallinity and well-dispersity, which may have wider applications than the aggregate ones obtained using conventional mechanochemical and Li+-imbibition methods.

Solvothermal one-step synthesis of Ni-Al layered double hydroxide/carbon nanotube/reduced graphene oxide sheet ternary nanocomposite with ultrahigh capacitance for supercapacitors.

PubMed

Yang, Wanlu; Gao, Zan; Wang, Jun; Ma, Jing; Zhang, Milin; Liu, Lianhe

2013-06-26

A Ni-Al layered double hydroxide (LDH), mutil-wall carbon nanotube (CNT), and reduced graphene oxide sheet (GNS) ternary nanocomposite electrode material has been developed by a facile one-step ethanol solvothermal method. The obtained LDH/CNT/GNS composite displayed a three-dimensional (3D) architecture with flowerlike Ni-Al LDH/CNT nanocrystallites gradually self-assembled on GNS nanosheets. GNS was used as building blocks to construct 3D nanostructure, and the LDH/CNT nanoflowers in turn separated the two-dimensional (2D) GNS sheets, which preserved the high surface area of GNSs. Furthermore, the generated porous networks with a narrow pore size distribution in the LDH/CNT/GNS composite were also demonstrated by the N2 adsorption/desorption experiment. Such morphology would be favorable to improve the mass transfer and electrochemical action of the electrode. As supercapacitor electrode material, the LDH/CNT/GNS hybrid exhibited excellent electrochemical performance, including ultrahigh specific capacitance (1562 F/g at 5 mA/cm(2)), excellent rate capability, and long-term cycling performance, which could be a promising energy storage/conversion material for supercapacitor application.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance.

PubMed

Yilmaz, Gamze; Yam, Kah Meng; Zhang, Chun; Fan, Hong Jin; Ho, Ghim Wei

2017-07-01

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co 9 S 8 ) system. The embedment of metal sulfide species (Co 9 S 8 ) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co 9 S 8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic-organic functional materials for electrochemical applications and beyond. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced graphene oxide modified NiFe-calcinated layered double hydroxides for enhanced photocatalytic removal of methylene blue

NASA Astrophysics Data System (ADS)

Zhao, Guoqing; Li, Caifeng; Wu, Xia; Yu, Jingang; Jiang, Xinyu; Hu, Wenjihao; Jiao, Feipeng

2018-03-01

Calcined layered double hydroxides (CLDH) are one of the remarkable photocatalysts passionately studied for photodecolorization of organic dyes. NiFe-CLDH was successfully modified by reduced graphene oxide (RGO) through a facile in situ crystallization technique. The obtained RGO/NiFe-CLDH composites were fully characterized by powder X-ray diffraction (XRD), Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FT-IR), and UV-vis diffuse reflectance spectroscopy (DRS). The results analysis indicated that RGO sheets could work as base course to prompt the growth of LDH crystallites and NiFe-LDH lamellar crystal promiscuously distributed on the sheets with a strong interplay between each other. The photocatalytic performance of RGO/NiFe-CLDH composites toward decolorization of methylene blue tightly depended on the mass fraction of RGO and calcinated temperature. At the RGO weight loading of 1%, calcination temperature of 500 °C, the photocatalytic degradation efficiency of RGO/NiFe-CLDH composites reached 93.0% within 5.0 h. The enhanced activity of RGO/NiFe-CLDH composites may be due to the concerted catalysis effect between two constituents of as-prepared composites.

Layered Double Hydroxides: Potential Release-on-Demand Fertilizers for Plant Zinc Nutrition.

PubMed

López-Rayo, Sandra; Imran, Ahmad; Bruun Hansen, Hans Chr; Schjoerring, Jan K; Magid, Jakob

2017-10-11

A novel zinc (Zn) fertilizer concept based on Zn-doped layered double hydroxides (Zn-doped Mg-Fe-LDHs) has been investigated. Zn-doped Mg-Fe-LDHs were synthesized, their chemical composition was analyzed, and their nutrient release was studied in buffered solutions with different pH values. Uptake of Zn by barley (Hordeum vulgare cv. Antonia) was evaluated in short- (8 weeks), medium- (11 weeks), and long-term (28 weeks) experiments in quartz sand and in a calcareous soil enriched with Zn-doped Mg-Fe-LDHs. The Zn release rate of the Zn-doped Mg-Fe-LDHs was described by a first-order kinetics equation showing maximum release at pH 5.2, reaching approximately 45% of the total Zn content. The Zn concentrations in the plants receiving the LDHs were between 2- and 9.5-fold higher than those in plants without Zn addition. A positive effect of the LDHs was also found in soil. This work documents the long-term Zn release capacity of LDHs complying with a release-on-demand behavior and serves as proof-of-concept that Zn-doped Mg-Fe-LDHs can be used as Zn fertilizers.

Gadolinium-Doped Gallic Acid-Zinc/Aluminium-Layered Double Hydroxide/Gold Theranostic Nanoparticles for a Bimodal Magnetic Resonance Imaging and Drug Delivery System

PubMed Central

Sani Usman, Muhammad; Hussein, Mohd Zobir; Fakurazi, Sharida; Ahmad Saad, Fathinul Fikri

2017-01-01

We have developed gadolinium-based theranostic nanoparticles for co-delivery of drug and magnetic resonance imaging (MRI) contrast agent using Zn/Al-layered double hydroxide as the nanocarrier platform, a naturally occurring phenolic compound, gallic acid (GA) as therapeutic agent, and Gd(NO3)3 as diagnostic agent. Gold nanoparticles (AuNPs) were grown on the system to support the contrast for MRI imaging. The nanoparticles were characterized using techniques such as Hi-TEM, XRD, ICP-ES. Kinetic release study of the GA from the nanoparticles showed about 70% of GA was released over a period of 72 h. The in vitro cell viability test for the nanoparticles showed relatively low toxicity to human cell lines (3T3) and improved toxicity on cancerous cell lines (HepG2). A preliminary contrast property test of the nanoparticles, tested on a 3 Tesla MRI machine at various concentrations of GAGZAu and water (as a reference) indicates that the nanoparticles have a promising dual diagnostic and therapeutic features to further develop a better future for clinical remedy for cancer treatment. PMID:28858229

An acetylcholinesterase biosensor based on graphene-gold nanocomposite and calcined layered double hydroxide.

PubMed

Zhai, Chen; Guo, Yemin; Sun, Xia; Zheng, Yuhe; Wang, Xiangyou

2014-05-10

In this study, a novel acetylcholinesterase-based biosensor was fabricated. Acetylcholinesterase (AChE) was immobilized onto a glassy carbon electrode (GCE) with the aid of Cu-Mg-Al calcined layered double hydroxide (CLDH). CLDH can provide a bigger effective surface area for AChE loading, which could improve the precision and stability of AChE biosensor. However, the poor electroconductibility of CLDHs could lead to the low sensitivity of AChE biosensor. In order to effectively compensate the disadvantages of CLDHs, graphene-gold nanocomposites were used for improving the electron transfer rate. Thus, the graphene-gold nanocomposite (GN-AuNPs) was firstly modified onto the GCE, and then the prepared CLDH-AChE composite was immobilized onto the modified GCE to construct a sensitive AChE biosensor for pesticides detection. Relevant parameters were studied in detail and optimized, including the pH of the acetylthiocholine chloride (ATCl) solution, the amount of AChE immobilized on the biosensor and the inhibition time governing the analytical performance of the biosensor. The biosensor detected chlorpyrifos at concentrations ranging from 0.05 to 150μg/L. The detection limit for chlorpyrifos was 0.05μg/L. Copyright © 2014 Elsevier Inc. All rights reserved.

Multifunctional organic–inorganic hybrid nanoparticles and nanosheets based on chitosan derivative and layered double hydroxide: cellular uptake mechanism and application for topical ocular drug delivery

PubMed Central

Chi, Huibo; Gu, Yan; Xu, Tingting; Cao, Feng

2017-01-01

To study the cellular uptake mechanism of multifunctional organic–inorganic hybrid nanoparticles and nanosheets, new chitosan–glutathione–valine–valine-layered double hydroxide (CG-VV-LDH) nanosheets with active targeting to peptide transporter-1 (PepT-1) were prepared, characterized and further compared with CG-VV-LDH nanoparticles. Both organic–inorganic hybrid nanoparticles and nanosheets showed a sustained release in vitro and prolonged precorneal retention time in vivo, but CG-VV-LDH nanoparticles showed superior permeability in the isolated cornea of rabbits than CG-VV-LDH nanosheets. Furthermore, results of cellular uptake on human corneal epithelial primary cells (HCEpiC) and retinal pigment epithelial (ARPE-19) cells indicated that both clathrin-mediated endocytosis and active transport of PepT-1 are involved in the internalization of CG-VV-LDH nanoparticles and CG-VV-LDH nanosheets. In summary, the CG-VV-LDH nanoparticle may be a promising carrier as a topical ocular drug delivery system for the treatment of ocular diseases of mid-posterior segments, while the CG-VV-LDH nanosheet may be suitable for the treatment of ocular surface diseases. PMID:28280329

Investigation of the dye-sensitized solar cell designed by a series of mixed metal oxides based on ZnAl-layered double hydroxide

NASA Astrophysics Data System (ADS)

Zhu, Yatong; Wang, Dali; Yang, Xiaoyu; Liu, Sha; Liu, Dong; Liu, Jie; Xiao, Hongdi; Hao, Xiaotao; Liu, Jianqiang

2017-10-01

In this paper, the anode materials for dye-sensitized solar cell (DSSC) were prepared by a facile calcination method using the ZnAl-layered double hydroxide (LDH) as a precursor. The ZnAl-LDHs with different molar ratios (Zn:Al = 2, 4, 6, 8) were prepared by the urea method and the mixed metal oxides (MMO) were prepared by calcining the LDHs at 500 °C. A series of cells were assembled by the corresponding MMOs and different dyes (N3 and N719). The basic parameters were investigated by X-ray diffraction, scanning electron microscope, thermogravimetric and differential thermal analysis, nitrogen sorption analysis and UV-Vis absorption spectrum. The photovoltaic performance of DSSCs was measured by electrochemical method. It could be seen that ZnAl molar ratios and different dyes had great influence on the efficiency of DSSC. The efficiency improved explicitly with increasing ZnAl molar ratio and the DSSC made of N3 showed better efficiency than that of N719. The best efficiency of N3 conditions reached 0.55% when the ratio of ZnAl-LDH precursor was 8:1.

8-Anilino-1-naphthalenesulfonate/Layered Double Hydroxide Ultrathin Films: Small Anion Assembly and Its Potential Application as a Fluorescent Biosensor.

PubMed

Zhang, Ping; Li, Ling; Zhao, Yun; Tian, Zeyun; Qin, Yumei; Lu, Jun

2016-09-06

The fluorescent dye 8-anilino-1-naphthalenesulfonate (ANS) is a widely used fluorescent probe molecule for biochemistry analysis. This paper reported the fabrication of ANS/layered double hydroxide nanosheets (ANS/LDH)n ultrathin films (UTFs) via the layer-by-layer small anion assembly technique based on electrostatic interaction and two possible weak interactions: hydrogen-bond and induced electrostatic interactions between ANS and positive-charged LDH nanosheets. The obtained UTFs show a long-range-ordered periodic layered stacking structure and weak fluorescence in dry air or water, but it split into three narrow strong peaks in a weak polarity environment induced by the two-dimensional (2D) confinement effect of the LDH laminate; the fluorescence intensity increases with decreasing the solvent polarity, concomitant with the blue shift of the emission peaks, which show good sensoring reversibility. Meanwhile, the UTFs exhibit selective fluorescence enhancement to the bovine serum albumin (BSA)-like protein biomolecules, and the rate of fluorescence enhancement with the protein concentration is significantly different with the different protein aggregate states. The (ANS/LDH)n UTF has the potential to be a novel type of biological flourescence sensor material.

Evaluation of layered double hydroxide/graphene hybrid as a sorbent in membrane-protected stir-bar supported micro-solid-phase extraction for determination of organochlorine pesticides in urine samples.

PubMed

Sajid, Muhammad; Basheer, Chanbasha; Daud, Muhammad; Alsharaa, Abdulnaser

2017-03-17

In this work, the potential of layered double hydroxide/graphene (LDH-G) hybrid as a sorbent for extraction and preconcentration of fifteen organochlorine pesticides (OCPs) in urine samples was evaluated. The LDH-G hybrid was synthesized by co-precipitation method and it was then characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The sorbent was then employed in membrane-protected stir-bar supported micro-solid-phase extraction (SB-μ-SPE) of OCPs in urine samples. This extraction approach is highly suitable for the samples representing matrix complexity such as urine because the sorbent is effectively protected inside the membrane. The extracted samples were analyzed by gas chromatography mass spectrometry. The factors that affect the performance of SB-μ-SPE were suitably optimized. This method demonstrated good linearity with coefficients of determination up to 0.9996. The limits of detection ranged between 0.22 and 1.38ngmL -1 . The RSD values for intra and inter-day precision were also in a satisfactory range (2.7-9.5%). Copyright © 2017 Elsevier B.V. All rights reserved.

Brain Targeting Delivery Facilitated by Ligand-Functionalized Layered Double Hydroxide Nanoparticles.

PubMed

Chen, Weiyu; Zuo, Huali; Zhang, Enqi; Li, Li; Henrich-Noack, Petra; Cooper, Helen; Qian, Yujin; Xu, Zhi Ping

2018-06-20

A delivery platform with highly selective permeability through the blood-brain barrier (BBB) is essential for brain disease treatment. In this research, we designed and prepared a novel target nanoplatform, that is, layered double hydroxide (LDH) nanoparticle conjugated with targeting peptide-ligand Angiopep-2 (Ang2) or rabies virus glycoprotein (RVG) via intermatrix bovine serum albumin for brain targeting. In vitro studies show that functionalization with the target ligand significantly increases the delivery efficiency of LDH nanoparticles to the brain endothelial (bEnd.3) cells and the transcytosis through the simulated BBB model, that is, bEnd.3 cell-constructed multilayer membrane. In vivo confocal neuroimaging of the rat's blood-retina area dynamically demonstrates that LDH nanoparticles modified with peptide ligands have shown a prolonged retention period within the retina vessel in comparison with the pristine LDH group. Moreover, Ang2-modified LDH nanoparticles are found to more specifically accumulate in the mouse brain than the control and RVG-modified LDH nanoparticles after 2 and 48 h intravenous injection. All these findings strongly suggest that Ang2-modified LDHs can serve as an effective targeting nanoplatform for brain disease treatment.

Innovative Linear Low Density Polyethylene Nanocomposite Films Reinforced with Organophilic Layered Double Hydroxides: Fabrication, Morphology and Enhanced Multifunctional Properties.

PubMed

Xie, Jiazhuo; Wang, Haijun; Wang, Zhou; Zhao, Qinghua; Yang, Yuechao; Waterhouse, Geoffrey I N; Hao, Lei; Xiao, Zihao; Xu, Jing

2018-01-08

Herein, we reported the successful development of novel nanocomposite films based on linear low density polyethylene (LLDPE) with enhanced anti-drop, optical, mechanical, thermal and water vapor barrier properties by introducing organophilic layered double hydroxides (OLDHs) nanosheets. OLDHs loadings were varied from 0-6 wt.%. Structural analyses using the Fourier transform infrared spectrum (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) indicated that the OLDHs nanosheets were homogeneously dispersed with an ordered alignment in the LLDPE matrix. The LLDPE film containing 2 wt.% OLDHs (denoted as OLDHs-2) showed the optimal mechanical, thermal and water vapor barrier properties, whilst the anti-drop and optical performance of the films improved with increasing OLDHs content. The enhanced antidrop properties of the composite films relative to pristine LLDPE can be expected to effectively reduce agricultural losses to disease when the films are applied as agricultural films, whilst the superior light transmittance and water-retaining properties of the composite films will boost agricultural production. Results presented suggest that multifunctional LLDPE/OLDHs nanocomposites show great promise as low cost agricultural plastic films.

Synthesis and characterization of graphene quantum dots/CoNiAl-layered double-hydroxide nanocomposite: Application as a glucose sensor.

PubMed

Samuei, Sara; Fakkar, Jila; Rezvani, Zolfaghar; Shomali, Ashkan; Habibi, Biuck

2017-03-15

In the present work, a novel nanocomposite based on the graphene quantum dots and CoNiAl-layered double-hydroxide was successfully synthesized by co-precipitation method. To achieve the morphological, structural and compositional information, the resulted nanocomposite was characterized by scanning electron microscopy X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and photoluminescence. Then, the nanocomposite was used as a modifier to fabricate a modified carbon paste electrode as a non-enzymatic sensor for glucose determination. Electrochemical behavior and determination of glucose at the nanocomposite modified carbon paste electrode were investigated by cyclic voltammetry and chronoamperometry methods, respectively. The prepared sensor offered good electrocatalytic properties, fast response time, high reproducibility and stability. At the optimum conditions, the constructed sensor exhibits wide linear range; 0.01-14.0 mM with a detection limit of 6 μM (S/N = 3) and high sensitivity of 48.717 μAmM -1 . Finally, the sensor was successfully applied to determine the glucose in real samples which demonstrated its applicability. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of Iodate in Food, Environmental, and Biological Samples after Solid-Phase Extraction with Ni-Al-Zr Ternary Layered Double Hydroxide as a Nanosorbent

PubMed Central

Abdolmohammad-Zadeh, Hossein; Tavarid, Keyvan; Talleb, Zeynab

2012-01-01

Nanostructured nickel-aluminum-zirconium ternary layered double hydroxide was successfully applied as a solid-phase extraction sorbent for the separation and pre-concentration of trace levels of iodate in food, environmental and biological samples. An indirect method was used for monitoring of the extracted iodate ions. The method is based on the reaction of the iodate with iodide in acidic solution to produce iodine, which can be spectrophotometrically monitored at 352 nm. The absorbance is directly proportional to the concentration of iodate in the sample. The effect of several parameters such as pH, sample flow rate, amount of nanosorbent, elution conditions, sample volume, and coexisting ions on the recovery was investigated. In the optimum experimental conditions, the limit of detection (3s) and enrichment factor were 0.12 μg mL−1 and 20, respectively. The calibration graph using the preconcentration system was linear in the range of 0.2–2.8 μg mL−1 with a correlation coefficient of 0.998. In order to validate the presented method, a certified reference material, NIST SRM 1549, was also analyzed. PMID:22619590

Operando NMR and XRD study of chemically synthesized LiCx oxidation in a dry room environment

DOE PAGES

Sacci, Robert L.; Gill, Lance W.; Hagaman, Edward W.; ...

2015-04-07

We test the stability of pre-lithiated graphite anodes for Li-ion batteries in a dry room battery processing room. The reaction between LiCx and laboratory air was followed using operando NMR and x-ray diffraction as these methods are sensitive to change in Li stoichiometry in graphite. There is minimal reactivity between LiC 6 and N 2, CO 2 or O 2; however, LiC 6 reacts with moisture to form lithium (hydr)oxide. The reaction rate follows zero-order kinetics with respects to intercalated lithium suggesting that lithium transport through the graphite is fast. The reaction mechanism occurs by sequential formation of higher stagesmore » LiC 12, then LiC 18, and then LiC 24 as the hydrolysis proceeds to the formation of Li xOH y and graphite end products. Slowing down the formation rate of the Li xOH y passivation layer stabilizes of the higher stages.« less

Kinetic and thermodynamic hysteresis imposed by intercalation of proflavine in ferrocene-modified double-stranded DNA.

PubMed

Gebala, Magdalena; La Mantia, Fabio; Schuhmann, Wolfgang

2013-07-22

Surface-confined immobilized redox species often do not show the expected zero peak separation in slow-scan cyclic voltammograms. This phenomenon is frequently associated to experimental drawbacks and hence neglected. However, a nonzero peak separation, which is common to many electrochemical systems with high structural flexibility, can be rationally assigned to a thermodynamic hysteresis. To study this phenomenon, a surface-confined redox species was used. Specifically, a DNA strand which is tagged with ferrocene (Fc) moieties at its 5' end and its complementary capture probe is thiolated at the 3' end was self-assembled in a monolayer at a Au electrode with the Fc moieties being located at the bottom plane of the double-stranded DNA (dsDNA). The DNA-bound Fc undergoes rapid electron transfer with the electrode surface as evaluated by fast scan cyclic voltammetry. The electron transfer is sensitive to the ion transport along the DNA strands, a phenomenon which is modulated upon specific intercalation of proflavine into surface-bound dsDNA. The electron transfer rate of the Fc(0/+) redox process is influenced by the cationic permselectivity of the DNA monolayer. In addition to the kinetic hindrance, a thermodynamic effect correlated with changes in the activity coefficients of the Fc(0/+) moieties near the gold-dsDNA interface is observed and discussed as source of the observed hysteresis causing the non-zero peak separation in the voltammograms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphite fiber intercalation: Dynamics of the bromine intercalation process

NASA Technical Reports Server (NTRS)

Jaworske, D. A.; Zinolabedini, R.

1985-01-01

The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

[Ru(phen)2DPPZ]2+ is in contact with DNA bases when it forms a luminescent complex with single-stranded oligonucleotides.

PubMed

Moon, Seok Joon; Kim, Jong Moon; Choi, Ji Youn; Kim, Seog K; Lee, Je Seung; Jang, Ho G

2005-05-01

The luminescence intensity of the Delta- and Lambda-enantiomer of [Ru(phen)2DPPZ]2+ ([Ru(phenanthroline)2 dipyrido[3,2-a:2',3'-c]phenazine]2+) complex enhanced upon binding to double stranded DNA, which has been known as "light switch effect". The enhancement of the luminescence required the intercalation of the large ligand between DNA base pairs. In this study, we report the enhancement in the luminescence intensity when the metal complexes bind to single stranded oligonucleotides, indicating that the "light switch effect" does not require intercalation of the large DPPZ ligand. Oligonucleotides may provide a hydrophobic cavity for the [Ru(phen)2DPPZ]2+ complex to prevent the quenching by the water molecule. In the cavity, the metal complex is in contact with DNA bases as is evidenced by the observation that the excited energy of the DNA bases transfer to the bound metal complex. However, the contact of the metal complex with DNA bases is different from the stacking of DPPZ in the intercalation pocket. In addition to the normal two luminescence lifetimes, a short lifetime in the range of 1-2 ns was found for both the delta- and lambda-enantiomer of [Ru(phen)2DPPZ]2+ when complexed with single stranded oligonucleotides, which may be assigned to the metal complex that is outside of the cavity, interacting with phosphate groups of DNA.

Tumor marker analyses from the phase III, placebo-controlled, FASTACT-2 study of intercalated erlotinib with gemcitabine/platinum in the first-line treatment of advanced non-small-cell lung cancer.

PubMed

Mok, Tony; Ladrera, Guia; Srimuninnimit, Vichien; Sriuranpong, Virote; Yu, Chong-Jen; Thongprasert, Sumitra; Sandoval-Tan, Jennifer; Lee, Jin Soo; Fuerte, Fatima; Shames, David S; Klughammer, Barbara; Truman, Matt; Perez-Moreno, Pablo; Wu, Yi-Long

2016-08-01

The FASTACT-2 study of intercalated erlotinib with chemotherapy in Asian patients found that EGFR mutations were the main driver behind the significant progression-free survival (PFS) benefit noted in the overall population. Further exploratory biomarker analyses were conducted to provide additional insight. This multicenter, randomized, placebo-controlled, double-blind, phase III study investigated intercalated first-line erlotinib or placebo with gemcitabine/platinum, followed by maintenance erlotinib or placebo, for patients with stage IIIB/IV non-small cell lung cancer (NSCLC). Provision of samples for biomarker analysis was encouraged but not mandatory. The following biomarkers were analyzed (in order of priority): EGFR mutation by cobas(®) test, KRAS mutation by cobas(®)KRAS test, HER2 by immunohistochemistry (IHC), HER3 by IHC, ERCC1 by IHC, EGFR gene copy number by fluorescence in-situ hybridization (FISH) and EGFR by IHC. All subgroups were assessed for PFS (primary endpoint), overall survival (OS), non-progression rate and objective response rate. Overall, 256 patients provided samples for analysis. Considerable overlap was noted among biomarkers, except for EGFR and KRAS mutations, which are mutually exclusive. Other than EGFR mutations (p<0.0001), no other biomarkers were significantly predictive of outcomes in a treatment-by-biomarker interaction test, although ERCC1 IHC-positive status was predictive of improved OS for the erlotinib arm versus placebo in EGFR wild-type patients (median 18.4 vs 9.5 months; hazard ratio [HR] HR=0.32, 95% confidence intervals [CI]: 0.14-0.69, p=0.0024). Activating EGFR mutations were predictive for improved treatment outcomes with a first-line intercalated regimen of chemotherapy and erlotinib in NSCLC. ERCC1 status may have some predictive value in EGFR wild-type disease, but requires further investigation. Copyright © 2016 The Authors. Published by Elsevier Ireland Ltd.. All rights reserved.

Safety and immunogenicity of inactivated poliovirus vaccine based on Sabin strains with and without aluminum hydroxide: a phase I trial in healthy adults.

PubMed

Verdijk, Pauline; Rots, Nynke Y; van Oijen, Monique G C T; Oberste, M Steven; Boog, Claire J; Okayasu, Hiromasa; Sutter, Roland W; Bakker, Wilfried A M

2013-11-12

An inactivated poliovirus vaccine (IPV) based on attenuated poliovirus strains (Sabin-1, -2 and -3) was developed for technology transfer to manufacturers in low- and middle income countries in the context of the Global Polio Eradication Initiative. Safety and immunogenicity of the Sabin-IPV was evaluated in a double-blind, randomized, controlled, phase I 'proof-of-concept' trial. Healthy male adults received a single intramuscular injection with Sabin-IPV, Sabin-IPV adjuvanted with aluminum hydroxide or conventional IPV. Virus-neutralizing titers against both Sabin and wild poliovirus strains were determined before and 28 days after vaccination. No vaccine-related serious adverse events were observed, and all local and systemic reactions were mild or moderate and transient. In all subjects, an increase in antibody titer for all types of poliovirus (both Sabin and wild strains) was observed 28 days after vaccination. Sabin-IPV and Sabin-IPV adjuvanted with aluminum hydroxide administered as a booster dose were equally immunogenic and safe as conventional IPV. EudraCTnr: 2010-024581-22, NCT01708720. Copyright © 2013 Elsevier Ltd. All rights reserved.

Doxorubicin hinders DNA condensation promoted by the protein bovine serum albumin (BSA).

PubMed

Lima, C H M; de Paula, H M C; da Silva, L H M; Rocha, M S

2017-12-01

In this work, we have studied the interaction between the anticancer drug doxorubicin (doxo) and condensed DNA, using optical tweezers. To perform this task, we use the protein bovine serum albumin (BSA) in the working buffer to mimic two key conditions present in the real intracellular environment: the condensed state of the DNA and the abundant presence of charged macromolecules in the surrounding medium. In particular, we have found that, when doxo is previously intercalated in disperse DNA, the drug hinders the DNA condensation process upon the addition of BSA in the buffer. On the other hand, when bare DNA is firstly condensed by BSA, doxo is capable to intercalate and to unfold the DNA condensates at relatively high concentrations. In addition, a specific interaction between BSA and doxo was verified, which significantly changes the chemical equilibrium of the DNA-doxo interaction. Finally, the presence of BSA in the buffer stabilizes the double-helix structure of the DNA-doxo complexes, preventing partial DNA denaturation induced by the stretching forces. © 2017 Wiley Periodicals, Inc.

Electrochemical detection of synthetic DNA and native 16S rRNA fragments on a microarray using a biotinylated intercalator as coupling site for an enzyme label.

PubMed

Zimdars, Andreas; Gebala, Magdalena; Hartwich, Gerhard; Neugebauer, Sebastian; Schuhmann, Wolfgang

2015-10-01

The direct electrochemical detection of synthetic DNA and native 16S rRNA fragments isolated from Escherichia coli is described. Oligonucleotides are detected via selective post-labeling of double stranded DNA and DNA-RNA duplexes with a biotinylated intercalator that enables high-specific binding of a streptavidin/alkaline phosphatase conjugate. The alkaline phosphatase catalyzes formation of p-aminophenol that is subsequently oxidized at the underlying gold electrode and hence enables the detection of complementary hybridization of the DNA capture strands due to the enzymatic signal amplification. The hybridization assay was performed on microarrays consisting of 32 individually addressable gold microelectrodes. Synthetic DNA strands with sequences representing six different pathogens which are important for the diagnosis of urinary tract infections could be detected at concentrations of 60 nM. Native 16S rRNA isolated from the different pathogens could be detected at a concentration of 30 fM. Optimization of the sensing surface is described and influences on the assay performance are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical and spectroscopic studies of the interaction of proflavine with DNA.

PubMed

Aslanoglu, Mehmet

2006-03-01

The interaction of proflavine with herring sperm DNA has been investigated by cyclic voltammetry and UV-Vis spectroscopy as well as viscosity measurements. Shifts in the peak potentials in cyclic voltammetry, spectral changes in UV absorption titration, an increase in viscosity of DNA and the results of the effect of ionic strength on the binding constant strongly support the intercalation of proflavine into the DNA double helix. The binding constant for the interaction between proflavine and DNA was K = 2.32 (+/- 0.41) x 10(4) M(-1) and the binding site size was 2.07 (+/- 0.1) base pairs, estimated in voltammetric measurements. The value of the binding site size was determined to be closer to that expected for a planar intercalating agent. The standard Gibbs free-energy change is ca. -24.90 kJ/mol at 25 degrees C, indicating the spontaneity of the binding interaction. The binding constant determined by UV absorption measurements was K = 2.20 (+/- 0.48) x 10(4) M(-1), which is very close to the value determined by cyclic voltammetry assuming that the binding equilibrium is static.

Dynamics of graphite fiber intercalation: In situ resistivity measurements with a four point probe

NASA Technical Reports Server (NTRS)

Jaworske, D. A.

1984-01-01

The dynamics of ferric chloride intercalation of single graphite fibers were studied, in situ, using a four point dc bridge. Measurements before, during and after the intercalation showed that the intercalation occurred within minutes at 200 C. Changes in fiber resistivity after exposure to air suggested hydration of the graphite intercalation compound. Deintercalation of the ferric chloride was initiated at temperatures in excess of 400 C. cycling the intercalant into and out of the graphite fiber gave no improvements in fiber resistivity. The activation energy of the ferric chloride intercalation reaction was found to be 17 + or - 4 kcal/mol 1 consistent with the concept of a preliminary nucleation step in the intercalation reaction.

A bionanohybrid ZnAl-NADS ecological pesticide as a treatment for soft rot disease in potato (Solanum tuberosum L.).

PubMed

Morales-Irigoyen, Erika Elizabeth; de Las Mercedes Gómez-Y-Gómez, Yolanda; Flores-Moreno, Jorge Luis; Franco-Hernández, Marina Olivia

2017-09-18

Pectobacterium carotovorum (Pc) is a phytopathogenic strain that causes soft rot disease in potato (Solanum tuberosum L.), resulting in postharvest losses. Chemical control is effective for managing this disease, but overdoses cause adverse effects. Because farmers insist on using chemical agents for crop protection, it is necessary to develop more effective pesticides in which the active compound released can be regulated. In this context, we proposed the synthesis of ZnAl-NADS, in which nalidixic acid sodium salt (NADS) is linked to a ZnAl-NO 3 layered double hydroxide (LDH) host as a nanocarrier. XRD, FT-IR, and SEM analyses confirmed the successful intercalation of NADS into the interplanar LDH space. The drug release profile indicated that the maximum release was completed in 70 or 170 min for free NADS (alone) or for NADS released from ZnAl-NADS, respectively. This slow release was attributed to strong electrostatic interactions between the drug and the anion exchanger. A modulated release is preferable to the action of the bulk NADS, showing increased effectiveness and minimizing the amount of the chemical available to pollute the soil and the water. The fitting data from modified Freundlich and parabolic diffusion models explain the release behavior of the NADS, suggesting that the drug released from ZnAl-NADS bionanohybrid was carried out from the interlamellar sites, according to the ion exchange diffusion process also involving intraparticle diffusion (coeffect). ZnAl-NADS was tested in vitro against Escherichia coli (Ec) and Pc and exhibited bacteriostatic and biocidal effects at 0.025 and 0.075 mg mL -1 , respectively. ZnAl-NADS was also tested in vivo as an ecological pesticide for combating potato soft rot and was found to delay typical disease symptoms. In conclusion, ZnAl-NADS can potentially be used to control pests, infestation, and plant disease.

Toxicity evaluation of zinc aluminium levodopa nanocomposite via oral route in repeated dose study

NASA Astrophysics Data System (ADS)

Kura, Aminu Umar; Cheah, Pike-See; Hussein, Mohd Zobir; Hassan, Zurina; Tengku Azmi, Tengku Ibrahim; Hussein, Nor Fuzina; Fakurazi, Sharida

2014-05-01

Nanotechnology, through nanomedicine, allowed drugs to be manipulated into nanoscale sizes for delivery to the different parts of the body, at the same time, retaining the valuable pharmacological properties of the drugs. However, efficient drug delivery and excellent release potential of these delivery systems may be hindered by possible untoward side effects. In this study, the sub-acute toxicity of oral zinc aluminium nanocomposite with and without levodopa was assessed using the Organization for Economic Co-operation and Development guidelines. No sign or symptom of toxicity was observed in orally treated rats with the nanocomposite at 5 and 500 mg/kg concentrations. Body weight gain, feeding, water intake, general survival and organosomatic index were not significantly different between control and treatment groups. Aspartate aminotransferase (AST) in 500 mg/kg levodopa nanocomposite (169 ± 30 U/L), 5 mg/kg levodopa nanocomposite (172 ± 49 U/L), and 500 mg/kg layered double hydroxides (LDH) nanocomposite (175 ± 25 U/L) were notably elevated compared to controls (143 ± 05 U/L); but the difference were not significant ( p > 0.05). However, the differences in aspartate aminotransferase/alanine aminotransferase (AST/ALT) ratio of 500 mg/kg levodopa nanocomposite (0.32 ± 0.12) and 500 mg/kg LDH nanocomposite (0.34 ± 0.12) were statistically significant ( p < 0.05) compared to the control (0.51 ± 0.07). Histology of the liver, spleen and brain was found to be of similar morphology in both control and experimental groups. The kidneys of 500-mg/kg-treated rats with levodopa nanocomposite and LDH nanocomposite were found to have slight inflammatory changes, notably leukocyte infiltration around the glomeruli. The ultra-structure of the neurons from the substantia nigra of nanocomposite-exposed group was similar to those receiving only normal saline. The observed result has suggested possible liver and renal toxicity in orally administered levodopa intercalated nanocomposite; it is also dose-dependent that needs further assessment.

The Synthesis and Characterization of Gold-Core/LDH-Shell Nanoparticles

NASA Astrophysics Data System (ADS)

Rearick, Colton

In recent years, the field of nanomedicine has progressed at an astonishing rate, particularly with respect to applications in cancer treatment and molecular imaging. Although organic systems have been the frontrunners, inorganic systems have also begun to show promise, especially those based upon silica and magnetic nanoparticles (NPs). Many of these systems are being designed for simultaneous therapeutic and diagnostic capabilities, thus coining the term, theranostics. A unique class of inorganic systems that shows great promise as theranostics is that of layered double hydroxides (LDH). By synthesis of a core/shell structures, e.g. a gold nanoparticle (NP) core and LDH shell, the multifunctional theranostic may be developed without a drastic increase in the structural complexity. To demonstrate initial proof-of-concept of a potential (inorganic) theranostic platform, a Au-core/LDH-shell nanovector has been synthesized and characterized. The LDH shell was heterogeneously nucleated and grown on the surface of silica coated gold NPs via a coprecipitation method. Polyethylene glycol (PEG) was introduced in the initial synthesis steps to improve crystallinity and colloidal stability. Additionally, during synthesis, fluorescein isothiocyanate (FITC) was intercalated into the interlayer spacing of the LDH. In contrast to the PEG stabilization, a post synthesis citric acid treatment was used as a method to control the size and short-term stability. The heterogeneous core-shell system was characterized with scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), dynamic light scattering (DLS), and powder x-ray diffraction (PXRD). A preliminary in vitro study carried out with the assistance of Dr. Kaushal Rege's group at Arizona State University was to demonstrate the endocytosis capability of homogeneously-grown LDH NPs. The DLS measurements of the core-shell NPs indicated an average particle size of 212nm. The PXRD analysis showed that PEG greatly improved the crystallinity of the system while simultaneously preventing aggregation of the NPs. The preliminary in vitro fluorescence microscopy revealed a moderate uptake of homogeneous LDH NPs into the cells.

Formation of intercalation compound of kaolinite-glycine via displacing guest water by glycine.

PubMed

Zheng, Wan; Zhou, Jing; Zhang, Zhenqian; Chen, Likun; Zhang, Zhongfei; Li, Yong; Ma, Ning; Du, Piyi

2014-10-15

The kaolinite-glycine intercalation compound was successfully formed by displacing intercalated guest water molecules in kaolinite hydrate as a precursor. The microstructure of the compound was characterized by X-ray diffraction, Fourier Transform Infrared Spectroscopy and Scanning Electron Microscope. Results show that glycine can only be intercalated into hydrated kaolinite to form glycine-kaolinite by utilizing water molecules as a transition phase. The intercalated glycine molecules were squeezed partially into the ditrigonal holes in the silicate layer, resulting in the interlayer distance of kaolinite reaching 1.03nm. The proper intercalation temperature range was between 20°C and 80°C. An intercalation time of 24h or above was necessary to ensure the complete formation of kaolinite-glycine. The highest intercalation degree of about 84% appeared when the system was reacted at the temperature of 80°C for 48h. There were two activation energies for the intercalation of glycine into kaolinite, one being 21kJ/mol within the temperature range of 20-65°C and the other 5.8kJ/mol between 65°C and 80°C. The intercalation degree (N) and intercalation velocity (v) of as a function of intercalation time (t) can be empirically expressed as N=-79.35e(-)(t)(/14.8)+80.1 and v=5.37e(-)(t)(/14.8), respectively. Copyright © 2014 Elsevier Inc. All rights reserved.

Recovery of Lithium from Geothermal Brine with Lithium–Aluminum Layered Double Hydroxide Chloride Sorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paranthaman, Mariappan Parans; Li, Ling; Luo, Jiaqi

In this paper, we report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloridemore » from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ~91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. Finally, the present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.« less

A comparative study of Ni-Mn layered double hydroxide/carbon composites with different morphologies for supercapacitors.

PubMed

Li, M; Liu, F; Zhang, X B; Cheng, J P

2016-11-02

A variety of carbon materials varying from 0D to 2D, i.e. 0D nanoparticles, 1D carbon nanotubes (CNTs) and 2D reduced graphene oxide (rGO) are selected to in situ combine with Ni-Mn layered double hydroxide (LDH) to prepare electrode materials for supercapacitors. Through a simple solution method, hierarchical Ni-Mn LDH/carbon composites can be easily fabricated. A comparative study is carried out on the sandwich-like LDH/rGO, flower-like LDH/carbon black, turbostratic-structured LDH/CNTs and ternary LDH/CNTs/rGO for their structure, morphology, porous properties and electrochemical performances. The results show that the ternary Ni-Mn LDH/CNTs/rGO composite yields the highest specific capacitance of 1268 F g -1 in 2 M KOH electrolyte and a long lifespan, exhibiting great potential for supercapacitor applications. Meanwhile, investigation on the influence of the cation species of MOH (M = Li + , Na + or K + ) and the alkali concentration of the KOH electrolyte illustrates that increasing the concentration of the KOH electrolyte can benefit the capacitive performance of the electrode and that NaOH shows great advantages as an electrolyte for the Ni-Mn LDH/CNTs/rGO electrode due to its high capacitance and small resistance.

Polyhedral-Like NiMn-Layered Double Hydroxide/Porous Carbon as Electrode for Enhanced Electrochemical Performance Supercapacitors.

PubMed

Yu, Mei; Liu, Ruili; Liu, Jianhua; Li, Songmei; Ma, Yuxiao

2017-11-01

Polyhedral-like NiMn-layered double hydroxide/porous carbon (NiMn-LDH/PC-x) composites are successfully synthesized by hydrothermal method (x = 1, 2 means different mass percent of porous carbon (PC) in composites). The NiMn-LDH/PC-1 composites possess specific capacitance 1634 F g -1 at a current density of 1 A g -1 , and it is much better than that of pure LDH (1095 F g -1 at 1 A g -1 ). Besides, the sample can retain 84.58% of original capacitance after 3000 cycles at 15 A g -1 . An asymmetric supercapacitor with NiMn-LDH/PC-1 as anode and activated carbon as cathode is fabricated, and the supercapacitor can achieve an energy density of 18.60 Wh kg -1 at a power density of 225.03 W kg -1 . The enhanced electrochemical performance attributes to the high faradaic pseudocapacitance of NiMn-LDH, the introduction of PC, and the 3D porous structure of LDH/PC-1 composites. The introduction of PC hinders serious agglomeration of LDH and further accelerates ions transport. The encouraging results indicate that these materials are one of the most potential candidates for energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile preparation of fluorescent layered double hydroxide polymeric composites through the photo-induced surface-initiated controlled living polymerization

NASA Astrophysics Data System (ADS)

Chen, Junyu; Liu, Meiying; Huang, Qiang; Jiang, Ruming; Huang, Hongye; Deng, Fengjie; Wen, Yuanqing; Tian, Jianwen; Zhang, Xiaoyong; Wei, Yen

2018-05-01

(Zn/Al) layered double hydroxide (LDH) based fluorescence probes have been facilely fabricated via photo-induced surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, which demonstrated green fluorescence, good biocompatibility and excellent dispersion performance in aqueous solution. The as prepared (Zn/Al)LDH polymeric composites were modified with 2-methacryloyloxyethyl phosphorylcholine (MPC), acrylic acid (AA) and diacroloyl-fluorescein (Ac-Fl). Among them, the comonomers MPC and AA were used to endow their water dispersibility, biocompatibility and potential drug carriers, while the Ac-Fl was served both as the fluorescence signal and photocatalyst for RAFT polymerization. A series of characterization methods, including 1H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, transmission electronic microscopy, thermogravimetric analyses, X-ray photoelectron spectroscopy were employed to conform the successful of surface modification of LDH through photo-induced surface-initiated RAFT polymerization. Besides, UV-vis absorption spectra and fluorescence spectra were adopted to evaluate the optical characteristics of as prepared (Zn/Al)LDH-co-Poly(MPC-AA-Fl) composites, which exhibited high intense green fluorescence. Furthermore, the endocytosis behavior indicates that (Zn/Al)LDH-co-Poly(MPC-AA-Fl) composites could be potentially used in cell imaging and even drug delivery application for their excellent biocompatibility and all advantages described above.

Phosphate recovery from wastewater using engineered superparamagnetic particles modified with layered double hydroxide ion exchangers.

PubMed

Drenkova-Tuhtan, Asya; Mandel, Karl; Paulus, Anja; Meyer, Carsten; Hutter, Frank; Gellermann, Carsten; Sextl, Gerhard; Franzreb, Matthias; Steinmetz, Heidrun

2013-10-01

An innovative nanocomposite material is proposed for phosphate recovery from wastewater using magnetic assistance. Superparamagnetic microparticles modified with layered double hydroxide (LDH) ion exchangers of various compositions act as phosphate adsorbers. Magnetic separation and chemical regeneration of the particles allows their reuse, leading to the successful recovery of phosphate. Based upon the preliminary screening of different LDH ion exchanger modifications for phosphate selectivity and uptake capacity, MgFe-Zr LDH coated magnetic particles were chosen for further characterization and application. The adsorption kinetics of phosphate from municipal wastewater was studied in dependence with particle concentration, contact time and pH. Adsorption isotherms were then determined for the selected particle system. Recovery of phosphate and regeneration of the particles was examined via testing a variety of desorption solutions. Reusability of the particles was demonstrated for 15 adsorption/desorption cycles. Adsorption in the range of 75-97% was achieved in each cycle after 1 h contact time. Phosphate recovery and enrichment was possible through repetitive application of the desorption solution. Finally, a pilot scale experiment was carried out by treating 125 L of wastewater with the particles in five subsequent 25 L batches. Solid-liquid separation on this scale was carried out with a high-gradient magnetic filter (HGMF). Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxidative desulfurization: kinetic modelling.

PubMed

Dhir, S; Uppaluri, R; Purkait, M K

2009-01-30

Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

PubMed Central

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-01-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field. PMID:26670467

Layered double hydroxide of Cd-Al/C for the Mineralization and De-coloration of Dyes in Solar and Visible Light Exposure

NASA Astrophysics Data System (ADS)

Khan, Shahid Ali; Khan, Sher Bahadar; Asiri, Abdullah M.

2016-11-01

Cd-Al/C layered double hydroxide (Cd-Al/C-LDH) and Cd-Sb/C nanocatalyst are reported here for the de-coloration and mineralization of organic dyes. These catalysts were largely characterized by FESEM, EDS, XRD, FTIR, XPS, PL and DRS. The diffuse reflectance data showed a band gap at 2.92 and 2.983 eV for Cd-Al/C-LDH and Cd-Sb/C respectively. The band gap suggested that both catalysts work well in visible range. The photoluminescence spectra indicated a peak at 623 nm for both the catalysts which further support the effectiveness of the respective catalyst in visible range. Both catalysts also showed good recyclability and durability till 4th cycle. Five dyes, acridine orange (AO), malachite green (MG), crystal violet (CV), congo red (CR) and methyl orange (MO) were used in this experiment. Various parameters of different light intensity such as visible, ultraviolet, sunlight and dark condition are observed for the de-coloration of these dyes. The de-coloration phenomenon was proceeded through adsorption assisted phot-degradation. The low cost, abundant nature, good recyclability and better dye removal efficiency make these catalysts suitable candidates for the de-coloration and mineralization of organic dyes.

Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives

PubMed Central

Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

2016-01-01

High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application. PMID:26951794

Layered Double Hydroxide Nanoplatelets with Excellent Tribological Properties under High Contact Pressure as Water-Based Lubricant Additives.

PubMed

Wang, Hongdong; Liu, Yuhong; Chen, Zhe; Wu, Bibo; Xu, Sailong; Luo, Jianbin

2016-03-08

High efficient and sustainable utilization of water-based lubricant is essential for saving energy. In this paper, a kind of layered double hydroxide (LDH) nanoplatelets is synthesized and well dispersed in water due to the surface modification with oleylamine. The excellent tribological properties of the oleylamine-modified Ni-Al LDH (NiAl-LDH/OAm) nanoplatelets as water-based lubricant additives are evaluated by the tribological tests in an aqueous environment. The modified LDH nanoplatelets are found to not only reduce the friction but also enhance the wear resistance, compared with the water-based cutting fluid and lubricants containing other particle additives. By adding 0.5 wt% LDH nanoplatelets, under 1.5 GPa initial contact pressure, the friction coefficient, scar diameter, depth and width of the wear track dramatically decrease by 83.1%, 43.2%, 88.5% and 59.5%, respectively. It is considered that the sufficiently small size and the excellent dispersion of NiAl-LDH/OAm nanoplatelets in water are the key factors, so as to make them enter the contact area, form a lubricating film and prevent direct collision of asperity peaks. Our investigations demonstrate that the LDH nanoplatelet as a water-based lubricant additive has a great potential value in industrial application.

Recovery of Lithium from Geothermal Brine with Lithium-Aluminum Layered Double Hydroxide Chloride Sorbents.

PubMed

Paranthaman, Mariappan Parans; Li, Ling; Luo, Jiaqi; Hoke, Thomas; Ucar, Huseyin; Moyer, Bruce A; Harrison, Stephen

2017-11-21

We report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloride from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ∼91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. The present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.

Holey nickel-cobalt layered double hydroxide thin sheets with ultrahigh areal capacitance

NASA Astrophysics Data System (ADS)

Zhi, Lei; Zhang, Wenliang; Dang, Liqin; Sun, Jie; Shi, Feng; Xu, Hua; Liu, Zonghuai; Lei, Zhibin

2018-05-01

Strong coupling of electroactive components on conductive carbonaceous matrix to fabricate flexible hybrid electrodes represents a promising approach towards high performance supercapacitors. This work reports the fabrication of holey nickel cobalt layered double hydroxide (NiCo-LDH) nanosheets that are vertically grown on the cotton cloth-derived activated textile carbon (aTC). The abundant nanoholes on the thin-sheet NiCo-LDH not only enhance the electrode efficiency for efficient Faradaic redox reactions but also facilitate access of electrolyte to the electrode surface, thus giving rise to 70% capacitance arising from their outer surface. As a result, the aTC-NiCo hybrid electrode is capable of simultaneously achieving extremely high areal capacitance (6.37 F cm-2), mass capacitance (525 F g-1) and volumetric capacitance (249 F cm-3) at a practical level of mass loading (6.72 mg cm-2). Moreover, a solid-state asymmetric capacitor built with aTC-NiCo as positive electrode and active carbon-coated on aTC as negative electrode can deliver a volumetric energy density of 7.4 mWh cm-3 at a power density of 103 mW cm-3, while preserving a superior power performance, satisfying cycling stability and good mechanical flexibility.

Gold Nanoclusters@Ru(bpy)₃²⁺-Layered Double Hydroxide Ultrathin Film as a Cathodic Electrochemiluminescence Resonance Energy Transfer Probe.

PubMed

Yu, Yingchang; Lu, Chao; Zhang, Meining

2015-08-04

Herein, it is the first report that a cathodic electrochemiluminescence (ECL) resonance energy transfer (ERET) system is fabricated by layer-by-layer (LBL) electrostatic assembly of CoAl layered double hydroxide (LDH) nanosheets with a mixture of blue BSA-gold nanoclusters (AuNCs) and Ru(bpy)3(2+) (denoted as AuNCs@Ru) on an Au electrode. The possible ECL mechanism indicates that the appearance of CoAl-LDH nanosheets generates a long-range stacking order of the AuNCs@Ru on an Au electrode, facilitating the occurrence of the ERET between BSA-AuNC donors and Ru(bpy)3(2+) acceptors on the as-prepared AuNCs@Ru-LDH ultrathin films (UTFs). Furthermore, it is observed that the cathodic ECL intensity can be quenched efficiently in the presence of 6-mercaptopurine (6-MP) in a linear range of 2.5-100 nM with a detection limit of 1.0 nM. On the basis of these interesting phenomena, a facile cathodic ECL sensor has successfully distinguished 6-MP from other thiol-containing compounds (e.g., cysteine and glutathione) in human serum and urine samples. The proposed sensing scheme opens a way for employing the layered UTFs as a platform for the cathodic ECL of Ru(bpy)3(2+).

Recovery of Lithium from Geothermal Brine with Lithium–Aluminum Layered Double Hydroxide Chloride Sorbents

DOE PAGES

Paranthaman, Mariappan Parans; Li, Ling; Luo, Jiaqi; ...

2017-10-27

In this paper, we report a three-stage bench-scale column extraction process to selectively extract lithium chloride from geothermal brine. The goal of this research is to develop materials and processing technologies to improve the economics of lithium extraction and production from naturally occurring geothermal and other brines for energy storage applications. A novel sorbent, lithium aluminum layered double hydroxide chloride (LDH), is synthesized and characterized with X-ray powder diffraction, scanning electron microscopy, inductively coupled plasma optical emission spectrometry (ICP-OES), and thermogravimetric analysis. Each cycle of the column extraction process consists of three steps: (1) loading the sorbent with lithium chloridemore » from brine; (2) intermediate washing to remove unwanted ions; (3) final washing for unloading the lithium chloride ions. Our experimental analysis of eluate vs feed concentrations of Li and competing ions demonstrates that our optimized sorbents can achieve a recovery efficiency of ~91% and possess excellent Li apparent selectivity of 47.8 compared to Na ions and 212 compared to K ions, respectively in the brine. Finally, the present work demonstrates that LDH is an effective sorbent for selective extraction of lithium from brines, thus offering the possibility of effective application of lithium salts in lithium-ion batteries leading to a fundamental shift in the lithium supply chain.« less

Two-Dimensional Layered Double Hydroxides for Reactions of Methanation and Methane Reforming in C1 Chemistry

PubMed Central

Li, Panpan; Altaf, Naveed; Zhu, Mingyuan; Li, Jiangbing; Dai, Bin; Wang, Qiang

2018-01-01

CH4 as the paramount ingredient of natural gas plays an eminent role in C1 chemistry. CH4 catalytically converted to syngas is a significant route to transmute methane into high value-added chemicals. Moreover, the CO/CO2 methanation reaction is one of the potent technologies for CO2 valorization and the coal-derived natural gas production process. Due to the high thermal stability and high extent of dispersion of metallic particles, two-dimensional mixed metal oxides through calcined layered double hydroxides (LDHs) precursors are considered as the suitable supports or catalysts for both the reaction of methanation and methane reforming. The LDHs displayed compositional flexibility, small crystal sizes, high surface area and excellent basic properties. In this paper, we review previous works of LDHs applied in the reaction of both methanation and methane reforming, focus on the LDH-derived catalysts, which exhibit better catalytic performance and thermal stability than conventional catalysts prepared by impregnation method and also discuss the anti-coke ability and anti-sintering ability of LDH-derived catalysts. We believe that LDH-derived catalysts are promising materials in the heterogeneous catalytic field and provide new insight for the design of advance LDH-derived catalysts worthy of future research. PMID:29385064

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Mg-Al and Zn-Fe layered double hydroxides used for organic species storage and controlled release.

PubMed

Seftel, E M; Cool, P; Lutic, D

2013-12-01

Layered double hydroxides (LDH) containing (Mg and Al) or (Zn and Fe) were prepared by coprecipitation at constant pH, using NaOH and urea as precipitation agents. The most pure LDH phase in the Zn/Fe system was obtained with urea and in Mg/Al system when using NaOH. The incorporation of phenyl-alanine (Phe) anions in the interlayer of the LDH was performed by direct coprecipitation, ionic exchange and structure reconstruction of the mixed oxide obtained by the calcination of the coprecipitated product at 400°C. The reconstruction method and the direct coprecipitation in a medium containing Phe in the initial mixture were less successful in terms of high yields of organic-mineral composite than the ionic exchange method. A spectacular change in sample morphology and yield in exchanged solid was noticed for the Zn3Fe sample obtained by ionic exchange for 6h with Phe solution. A delivery test in PBS of pH=7.4 showed the release of the Phe in several steps up to 25 h indicating different host-guest interactions between the Phe and the LDH matrix. This behavior makes the preparation useful to obtain late delivery drugs, by the incorporation of the anion inside the LDH layer. © 2013.

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

NASA Astrophysics Data System (ADS)

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-12-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field.

Removal of As(V) and Sb(V) in aqueous solution by Mg/Al-layered double hydroxide-incorporated polyethersulfone polymer beads (PES-LDH).

PubMed

Lee, Sang-Ho; Choi, Heechul; Kim, Kyoung-Woong

2018-03-13

To develop a novel granular adsorbent to remove arsenic and antimony from water, calcined Mg/Al-layered double-hydroxide (CLDH)-incorporated polyethersulfone (PES) granular adsorbents (PES-LDH) were prepared using a core-shell method having 25% PES in an N,N-dimethylformamide solution. The PES-LDH displayed a spherical hollow shape having a rough surface and the average particle size of 1-2 mm. On the PES-LDH surface, nanosized CLDH (100-150 nm) was successfully immobilized by consolidation between PES and CLDH. The adsorption of Sb(V) by PES-LDH was found to be more favorable than for As(V), with the maximum adsorption capacity of As(V) and Sb(V) being 7.44 and 22.8 mg/g, respectively. The regeneration results indicated that a 0.5 M NaOH and 5 M NaCl mixed solution achieved an 80% regeneration efficiency in As(V) adsorption and desorption. However, the regeneration efficiency of Sb(V) gradually decreased due to its strong binding affinity, even though the PES-LDH showed much higher Sb(V) adsorption efficiency than As(V). This study suggested that PES-LDH could be a promising granular adsorbent for the remediation of As(V) and Sb(V) contained in wastewater.

Fast electrosynthesis of Fe-containing layered double hydroxide arrays toward highly efficient electrocatalytic oxidation reactions† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02417j

PubMed Central

Li, Zhenhua; An, Hongli; Wang, Zixuan; Xu, Simin; Evans, David G.; Duan, Xue

2015-01-01

A new electrochemical synthesis route was developed for the fabrication of Fe-containing layered double hydroxide (MFe-LDHs, M = Ni, Co and Li) hierarchical nanoarrays, which exhibit highly-efficient electrocatalytic performances for the oxidation reactions of several small molecules (water, hydrazine, methanol and ethanol). Ultrathin MFe-LDH nanoplatelets (200–300 nm in lateral length; 8–12 nm in thickness) perpendicular to the substrate surface are directly prepared within hundreds of seconds (<300 s) under cathodic potential. The as-obtained NiFe-LDH nanoplatelet arrays display promising behavior in the oxygen evolution reaction (OER), giving rise to a rather low overpotential (0.224 V) at 10.0 mA cm–2 with largely enhanced stability, much superior to previously reported electro-oxidation catalysts as well as the state-of-the-art Ir/C catalyst. Furthermore, the MFe-LDH nanoplatelet arrays can also efficiently catalyze several other fuel molecules’ oxidation (e.g., hydrazine, methanol and ethanol), delivering a satisfactory electrocatalytic activity and a high operation stability. In particular, this preparation method of Fe-containing LDHs is amenable to fast, effective and large-scale production, and shows promising applications in water splitting, fuel cells and other clean energy devices. PMID:29435211

Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene.

PubMed

Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2016-05-21

Ni(2+)Mn(3+) layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni(2+)/Mn(2+) salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.

Bacteria encapsulated in layered double hydroxides: towards an efficient bionanohybrid for pollutant degradation.

PubMed

Halma, Matilte; Mousty, Christine; Forano, Claude; Sancelme, Martine; Besse-Hoggan, Pascale; Prevot, Vanessa

2015-02-01

A soft chemical process was successfully used to immobilize Pseudomonas sp. strain ADP (ADP), a well-known atrazine (herbicide) degrading bacterium, within a Mg2Al-layered double hydroxide host matrix. This approach is based on a simple, quick and ecofriendly direct coprecipitation of metal salts in the presence of a colloidal suspension of bacteria in water. It must be stressed that by this process the mass ratio between inorganic and biological components was easily tuned ranging from 2 to 40. This ratio strongly influenced the biological activity of the bacteria towards atrazine degradation. The better results were obtained for ratios of 10 or lower, leading to an enhanced atrazine degradation rate and percentage compared to free cells. Moreover the biohybrid material maintained this biodegradative activity after four cycles of reutilization and 3 weeks storage at 4°C. The ADP@MgAl-LDH bionanohybrid materials were completely characterized by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis and scanning and transmission electronic microscopy (SEM and TEM) evidencing the successful immobilization of ADP within the inorganic matrix. This synthetic approach could be readily extended to other microbial whole-cell immobilization of interest for new developments in biotechnological systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Ethanol Sensor of CdO/Al2O3/CeO2 Obtained from Ce-DOPED Layered Double Hydroxides with High Response and Selectivity

NASA Astrophysics Data System (ADS)

Xu, Dongmei; Guan, Meiyu; Xu, Qinghong; Guo, Ying; Wang, Yao

2013-04-01

In this paper, Ce-doped CdAl layered double hydroxide (LDH) was first synthesized and the derivative CdO/Al2O3/CeO2 composite oxide was prepared by calcining Ce-doped CdAl LDH. The structure, morphology and chemical state of the Ce doped CdAl LDH and CdO/Al2O3/CeO2 were also investigated by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), solid state nuclear magnetic resonance (SSNMR), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The gas sensing properties of CdO/Al2O3/CeO2 to ethanol were further studied and compared with CdO/Al2O3 prepared from CdAl LDH, CeO2 powder as well as the calcined Ce salt. It turns out that CdO/Al2O3/CeO2 sensor shows best performance in ethanol response. Besides, CdO/Al2O3/CeO2 possesses short response/recovery time (12/72 s) as well as remarkable selectivity in ethanol sensing, which means composite oxides prepared from LDH are very promising in gas sensing application.

A mechanochemical approach to get stunningly uniform particles of magnesium-aluminum-layered double hydroxides

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqing; Qi, Fenglin; Li, Shuping; Wei, Shaohua; Zhou, Jiahong

2012-10-01

A mechanochemical approach is developed in preparing a series of magnesium-aluminum-layered double hydroxides (Mg-Al-LDHs). This approach includes a mechanochemical process which involved manual grinding of solid salts in an agate mortar and afterwards peptization process. In order to verify the LDHs structure synthesized in the grinding process, X-ray diffraction (XRD) patterns, transmission electron microscopy (TEM) photos and thermogravimetry/differential scanning calorimetry (TG-DSC) property of the product without peptization were characterized and the results show that amorphous particles with low crystallinity and poor thermal stability are obtained, and the effect of peptization is to improve the properties, more accurately, regular particles with high crystallinity and good thermal stability can be gained after peptization. Furthermore, the fundamental experimental parameters including grinding time, the molar ratio of Mg to Al element (defined as R value) and the water content were systematically examined in order to control the size and morphologies of LDHs particles, regular hexagonal particles or the spherical nanostructures can be efficiently obtained and the particle sizes were controlled in the range of 52-130 nm by carefully adjusting these parameters. At last, stunningly uniform Mg-Al-LDHs particles can be synthesized under proper R values, suitable grinding time and high degree of supersaturation.

In vivo pharmacological evaluation and efficacy study of methotrexate-encapsulated polymer-coated layered double hydroxide nanoparticles for possible application in the treatment of osteosarcoma.

PubMed

Ray, Sayantan; Saha, Suman; Sa, Biswanath; Chakraborty, Jui

2017-04-01

Considering the existing drawbacks of methotrexate (MTX) with respect to its solubility and toxicity, we incorporated it in a nanoceramic matrix, Mg-Al-layered double hydroxide (LDH) to form LDH-MTX nanoparticles, and the same was in turn encapsulated in a nontoxic and biodegradable polymer, poly (D,L-lactide-co-glycolide) (PLGA), to arrest the initial burst release and dose-dumping-related toxicity, already reported by our group. Our present study was designed to evaluate the pharmacokinetics, tissue distribution, survival rate of the test animals, and antitumor efficacy of the PLGA-LDH-MTX nanoparticles and its counterpart without LDH, PLGA-MTX nanoparticles compared with bare MTX. The median lethal dose (LD 50 ) of the former was higher, compared with bare MTX, using Balb/c nude mice, indicating it to be completely safe for use. Also, a comparative pharmacokinetic and antitumour efficacy study using MTX, PLGA-MTX, and PLGA-LDH-MTX nanoparticles in osteosarcoma-induced Balb/c nude mice in vivo demonstrated superiority of PLGA-LDH-MTX as compared to PLGA-MTX and bare MTX. The results suggest that PLGA-LDH-MTX nanoparticles might exhibit potential advantages over the present-day chemotherapy over bare MTX, for the possibility of treatment of osteosarcoma.

Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios.

PubMed

Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Gaston, Lewis A; Lahori, Altaf Hussain; Mahar, Amanullah

2016-07-15

Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

In-situ growth of ZIF-8 on layered double hydroxide: Effect of Zn/Al molar ratios on their structural, morphological and adsorption properties.

PubMed

Yang, Yingli; Yan, Xinlong; Hu, Xiaoyan; Feng, Rui; Zhou, Min

2017-11-01

In-situ growth of Zeolite imidazolate frameworks (ZIFs) on layered double hydroxides (LDHs) to form porous composites is a promising and challenging strategy to develop materials for separation application. Herein, the Zn-Al LDH with different Zn/Al molar ratios was prepared and used as matrix for the growth of ZIF-8 on its surface. The resulting composites were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N 2 physisorption, thermogravimetric (TG), scanning electron microscope (SEM) and elemental analysis followed by testing for As V removal from aqueous solution. Results showed that ZIF-8 could form on the surface of LDH with different Zn/Al molar ratios. At low Zn/Al molar ratios, the morphology and surface area of the ZIF/LDH composites and the content of ZIF-8 in the composites were little affected by the Zn/Al molar ratio. With increasing Zn/Al molar ratio, ZIF-8/LDH exhibited a lower surface area, which resulted from reduced content of ZIF-8 caused by impurities generated in the LDH matrix. All ZIF-8/LDH samples showed high As V adsorption capacity, which was significantly higher than that of pure LDH or ZIF-8. Copyright © 2017 Elsevier Inc. All rights reserved.

SBA-15/hydrotalcite nanocomposite as an efficient support for the immobilization of heteropolyacid: A triply-hybrid catalyst for the synthesis of 2-amino-4H-pyrans in water

NASA Astrophysics Data System (ADS)

Sadjadi, Samahe; Heravi, Majid M.; Zadsirjan, Vahideh; Farzaneh, Vahid

2017-12-01

To circumvent the high solubility and low surface area of heteropolyacid and in attempt to develop a bi-functional heterogeneous catalyst for promoting organic transformations, heteropolyacid was embedded in functionalized SBA-15 and subsequently hybridized with layered double hydroxide. The catalyst could be considered as a bi-functional catalyst with both acidic and basic properties. The acidic properties emerged from the SBA-15 and heteropolyacid component while layered double hydroxide render the catalyst basic. The catalyst was characterized by using SEM/EDX, FT-IR, XRD, ICP-AES, BET and elemental mapping analysis. The catalytic activity of the catalyst was studied for promoting one-pot three-component condensation of aromatic aldehydes, malononitrile or ethyl cyanoacetate and C-H activated acidic molecules in aqueous media for the synthesis of 2-amino-4H-pyran derivatives. The catalyst exhibited high catalytic activity, which was superior to the previously reported ones. Moreover, the reusability of the catalyst was excellent and the leaching of heteropolyacid was dramatically suppressed. High yields, short reaction times, eco-friendly conditions, simplicity of the procedure, reusability of the catalyst and broad substrate scope are the merits of this protocol.

⁹⁹mTc pyrene derivative complex causes double-strand breaks in dsDNA mainly through cluster-mediated indirect effect in aqueous solution.

PubMed

Chung, Wei-Ju; Cui, Yujia; Huang, Feng-Yun J; Tu, Tzu-Hui; Yang, Tzu-Sen; Lo, Jem-Mau; Chiang, Chi-Shiun; Hsu, Ian C

2014-01-01

Radiation therapy for cancer patients works by ionizing damage to nuclear DNA, primarily by creating double-strand breaks (DSB). A major shortcoming of traditional radiation therapy is the set of side effect associated with its long-range interaction with nearby tissues. Low-energy Auger electrons have the advantage of an extremely short effective range, minimizing damage to healthy tissue. Consequently, the isotope ⁹⁹mTc, an Auger electron source, is currently being studied for its beneficial potential in cancer treatment. We examined the dose effect of a pyrene derivative ⁹⁹mTc complex on plasmid DNA by using gel electrophoresis in both aqueous and methanol solutions. In aqueous solutions, the average yield per decay for double-strand breaks is 0.011±0.005 at low dose range, decreasing to 0.0005±0.0003 in the presence of 1 M dimethyl sulfoxide (DMSO). The apparent yield per decay for single-strand breaks (SSB) is 0.04±0.02, decreasing to approximately a fifth with 1 M DMSO. In methanol, the average yield per decay of DSB is 0.54±0.06 and drops to undetectable levels in 2 M DMSO. The SSB yield per decay is 7.2±0.2, changing to 0.4±0.2 in the presence of 2 M DMSO. The 95% decrease in the yield of DSB in DMSO indicates that the main mechanism for DSB formation is through indirect effect, possibly by cooperative binding or clustering of intercalators. In the presence of non-radioactive ligands at a near saturation concentration, where radioactive Tc compounds do not form large clusters, the yield of SSB stays the same while the yield of DSB decreases to the value in DMSO. DSBs generated by ⁹⁹mTc conjugated to intercalators are primarily caused by indirect effects through clustering.

Synthesis and electrical characterization of magnetic bilayer graphene intercalate.

PubMed

Kim, Namdong; Kim, Kwang S; Jung, Naeyoung; Brus, Louis; Kim, Philip

2011-02-09

We report synthesis and transport properties of the minimal graphite intercalation compound, a ferric chloride (FeCl(3))(n) island monolayer inside bilayer graphene. Chemical doping by the intercalant is simultaneously probed by micro-Raman spectroscopy and Hall measurements. Quantum oscillations of conductivity originate from microscopic domains of intercalated and unintercalated regions. A slight upturn in resistance related to magnetic transition is observed. Two-dimensional intercalation in bilayer graphene opens new possibilities to engineer two-dimensional properties of intercalates.

Interaction of small molecules with double-stranded RNA: spectroscopic, viscometric, and calorimetric study of hoechst and proflavine binding to PolyCG structures.

PubMed

Sinha, Rangana; Hossain, Maidul; Kumar, Gopinatha Suresh

2009-04-01

Design and synthesis of new small molecules binding to double-stranded RNA necessitate complete understanding of the molecular aspects of the binding of many existing molecules. Toward this goal, in this work we evaluated the biophysical aspects of the interaction of a DNA intercalator (proflavine) and a minor groove binder (hoechst 33258) with two polymorphic forms of polyCG, namely, the right-handed Watson-Crick base paired A-form and the left-handed Hoogsteen base paired H(L)-form, by absorption, fluorescence, and viscometry experiments. The energetics of the interaction of these molecules with the RNA structures has also been elucidated by isothermal titration calorimetry (ITC). Results suggest that proflavine strongly intercalates in both forms of polyCG, whereas hoechst shows mainly groove-binding modes. The binding of both drugs to both forms of RNA resulted in significant conformational change to the RNA structure with the bound molecules being placed in the chiral RNA helix. ITC profiles for both proflavine and hoechst show two binding sites. Binding of proflavine to both forms of RNA is endothermic and entropy driven in the first site and exothermic and enthalpy driven in the second site, whereas hoechst binding to both forms of RNA is exothermic and enthalpy driven in the first site and endothermic and entropy driven in the second site. This study suggests that the binding affinity characteristics and energetics of interaction of these DNA binding molecules with the RNA conformations are significantly different and may serve as data for future development of effective structure-selective RNA-based drugs.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

Energy and fuels from electrochemical interfaces

NASA Astrophysics Data System (ADS)

Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.; Markovic, Nenad M.

2017-01-01

Advances in electrocatalysis at solid-liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.

3D flower-like hierarchical Ag@nickel-cobalt hydroxide microsphere with enhanced electrochemical properties

NASA Astrophysics Data System (ADS)

Lv, Zijian; Zhong, Qin; Bu, Yunfei; Wu, Junpeng

2016-10-01

The morphology and electrical conductivity are essential to electrochemical performance of electrode materials in renewable energy conversion and storage technologies such as fuel cells and supercapacitors. Here, we explored a facile method to grow Ag@nickel-cobalt layered double hydroxide (Ag@Ni/Co-LDHs) with 3D flower-like microsphere structure. The results show the morphology of Ni/Co-LDHs varies with the introduction of Ag species. The prepared Ag@Ni/Co-LDHs not only exhibits an open hierarchical structure with high specific capacitance but also shows good electrical conductivity to support fast electron transport. Benefiting from the unique structural features, these flower-like Ag@Ni/Co-LDHs microspheres have impressive specific capacitance as high as 1768 F g-1 at 1 A g-1. It can be concluded that engineering the structure of the electrode can increase the efficiency of the specific capacitance as a battery-type electrode for hybrid supercapacitors.

Three-dimensional cotton-like nickel nanowire@Ni-Co hydroxide nanosheet arrays as binder-free electrode for high-performance asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Wan, Houzhao; Li, Lang; Xu, Yang; Tan, Qiuyang; Liu, Xiang; Zhang, Jun; Wang, Hanbin; Wang, Hao

2018-05-01

Three-dimensional (3D) cotton-like Ni-Co layered double hydroxide nanosheet arrays/nickel nanowires (3D Ni-Co LDH/NiNw) were successfully fabricated through a facile chemical bath deposition method. The 3D nickel nanowires are used as a conductive substrate with robust adhesion for high-pseudocapacitance Ni-Co LDH. The 3D Ni-Co LDH/NiNw electrode shows a high areal specific capacitance of 14 F cm-2 at 5 mA cm-2 and quality specific capacitance of 466.6 F g-1 at 0.125 A g-1 with respect to the whole quality of the electrode. The fabricated asymmetric supercapacitor exhibits a remarkable energy density of 0.387 mWh cm-2 using Ni-Co LDH/NiNw as the negative electrode. This high-performance composite electrode presents a new and affordable general approach for supercapacitors.

Three-dimensional cotton-like nickel nanowire@Ni-Co hydroxide nanosheet arrays as binder-free electrode for high-performance asymmetric supercapacitor.

PubMed

Wan, Houzhao; Li, Lang; Xu, Yang; Tan, Qiuyang; Liu, Xiang; Zhang, Jun; Wang, Hanbin; Wang, Hao

2018-05-11

Three-dimensional (3D) cotton-like Ni-Co layered double hydroxide nanosheet arrays/nickel nanowires (3D Ni-Co LDH/NiNw) were successfully fabricated through a facile chemical bath deposition method. The 3D nickel nanowires are used as a conductive substrate with robust adhesion for high-pseudocapacitance Ni-Co LDH. The 3D Ni-Co LDH/NiNw electrode shows a high areal specific capacitance of 14 F cm -2 at 5 mA cm -2 and quality specific capacitance of 466.6 F g -1 at 0.125 A g -1 with respect to the whole quality of the electrode. The fabricated asymmetric supercapacitor exhibits a remarkable energy density of 0.387 mWh cm -2 using Ni-Co LDH/NiNw as the negative electrode. This high-performance composite electrode presents a new and affordable general approach for supercapacitors.

Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

NASA Astrophysics Data System (ADS)

Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

2018-04-01

The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

The electric double layer at a metal electrode in pure water

NASA Astrophysics Data System (ADS)

Brüesch, Peter; Christen, Thomas

2004-03-01

Pure water is a weak electrolyte that dissociates into hydronium ions and hydroxide ions. In contact with a charged electrode a double layer forms for which neither experimental nor theoretical studies exist, in contrast to electrolytes containing extrinsic ions like acids, bases, and solute salts. Starting from a self-consistent solution of the one-dimensional modified Poisson-Boltzmann equation, which takes into account activity coefficients of point-like ions, we explore the properties of the electric double layer by successive incorporation of various correction terms like finite ion size, polarization, image charge, and field dissociation. We also discuss the effect of the usual approximation of an average potential as required for the one-dimensional Poisson-Boltzmann equation, and conclude that the one-dimensional approximation underestimates the ion density. We calculate the electric potential, the ion distributions, the pH-values, the ion-size corrected activity coefficients, and the dissociation constants close to the electric double layer and compare the results for the various model corrections.