Nanolayered composite with enhanced ultraviolet ray absorption properties from simultaneous intercalation of sunscreen molecules.

INTRODUCTION: The potential of layered double hydroxide (LDH) as a host of multiple ultraviolet-ray absorbers was investigated by simultaneous intercalation of benzophenone 4 (B4) and Eusolex® 232 (EUS) in Zn/Al LDH. METHODS: The nanocomposites were prepared via coprecipitation method at various molar ratios of B4 and EUS. RESULTS: At equal molar ratios, the obtained nanocomposite showed an intercalation selectivity that is preferential to EUS. However, the selectivity ratio of intercalated anions was shown to be capable of being altered by adjusting the molar ratio of intended guests during synthesis. Dual-guest nanocomposite synthesized with B4:EUS molar ratio 3:1 (ZEB [3:1]) showed an intercalation selectivity ratio of B4:EUS =53:47. Properties of ZEB (3:1) were monitored using powder X-ray diffractometer to show a basal spacing of 21.8 Å. Direct-injection mass spectra, Fourier transform infrared spectra, and ultraviolet-visible spectra confirmed the dual intercalation of both anions into the interlayer regions of dual-guest nanocomposite. The cytotoxicity study of dual-guest nanocomposite ZEB (3:1) on human dermal fibroblast cells showed no significant toxicity until 25 µg/mL. CONCLUSION: Overall, the findings demonstrate successful customization of ultraviolet-ray absorbers composition in LDH host.

Evaluation of Controlled-Release Property and Phytotoxicity Effect of Insect Pheromone Zinc-Layered Hydroxide Nanohybrid Intercalated with Hexenoic Acid.

A controlled release formulation for the insect pheromone hexenoic acid (HE) was successfully developed using zinc-layered hydroxide (ZLH) as host material through a simple coprecipitation technique, resulting in the formation of inorganic-organic nanolayered material with sustained release properties. The release of HE from its nanohybrid was found to occur in a controlled manner, governed by a pseudo-second order kinetics model. The maximum amount of HE released from the nanocomposite into solutions at pH 4, 6.5, and 8 was found to be 84, 73, and 83% for 1100 min, respectively. The hexenoate zinc-layered hydroxide nanomaterial (HEN) was found to be nontoxic for plants when green beans and wheat seeds were successfully germinated in all HEN concentrations tested in the experiment, with higher percentage of seed germination and higher radical seed growth as compared to its counter anion, HE. ZLH can be a promising carrier for insect pheromone toward a new generation of environmentally safe pesticide nanomaterial for crop protection.

Optimization of UV absorptivity of layered double hydroxide by intercalating organic UV-absorbent molecules.

Intercalation of Zn/Al layered double hydroxide (LDH) with benzophenone 9 (B9), a strong ultraviolet (UV) absorber, had been carried out by two different routes; co-precipitation and ion exchange method. Powder X-ray diffraction (PXRD) patterns of co-precipitated (ZB9C) and ion exchanged product (ZB91) showed basal spacing of 15.9 angstrom and 16.6 angstrom, respectively, as a result of the intercalation of B9 anions into the lamellae spaces of LDH. Intercalation was further confirmed by Fourier transform infrared spectra (FTIR), carbon, hydrogen, nitrogen and sulfur (CHNS) and thermogravimetric and differential thermogravimetric (TGA/DTG) studies. UV-vis absorption properties of the nanocomposite was investigated with diffuse reflectance UV-visible spectrometer and showed broader UV absorption range. Furthermore, stability of sunscreen molecules in LDH interlayer space was tested in deionized water, artificial sea water and skin pH condition to show slow deintercalation and high retention in host. Cytotoxicity study of the synthesized nanocomposites on human dermal fibroblast (HDF) cells shows no significant cytotoxicity after 24 h exposure for test concentrations up to 25 microg/mL.

3,4-Dichlorophenoxyacetate interleaved into anionic clay for controlled release formulation of a new environmentally friendly agrochemical.

A new layered organic-inorganic nanohybrid material, zinc-aluminum-3,4-dicholorophenoxyacetate (N3,4-D) in which an agrochemical, 3,4-dichlorophenoxyacetic acid (3,4-D), is intercalated into zinc-aluminum-layered double hydroxide (ZAL), was synthesized by coprecipitation method. A well-ordered nanomaterial was formed with a percentage loading of 53.5% (w/w). Due to the inclusion of 3,4-D, basal spacing expanded from 8.9 Å in ZAL to 18.7 Å in N3,4-D. The Fourier transform infrared study shows that the absorption bands of the resulting nanohybrid composed of both the 3,4-D and ZAL further confirmed the intercalation episode. Thermal analysis shows that ZAL host enhances the thermal stability of 3,4-D. Controlled-release experiment shows that the release of 3,4-D in the aqueous media is in the order of phosphate > carbonate > sulfate > chloride. These studies demonstrate the successful intercalation of the 3,4-D and its controlled release property in various aqueous media.

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

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.

Effect of incoming and outgoing exchangeable anions on the release kinetics of phenoxyherbicides nanohybrids.

The release of chlorophenoxyherbicides agrochemicals, namely 2-chloro- (2CPA), 4-chloro and 2,4,5-trichloro (TCPA) phenoxyacetates from their nanohybrids into various aqueous solutions; carbonate, sulfate and chloride was found to be controlled by pseudo-second order rate expression. The percentage saturated released was found to be anionic-dependent, in the order of carbonate>sulfate>chloride for the release media and 2CPA>4CPA>TCPA for the anionic guests. This study demonstrates that the release of the phenoxyherbicides agrochemicals from the nanohybrid compounds can be tuned by choosing the right combination of exchangeable anions both the incoming and the outgoing anions.

Synthesis of 4-chlorophenoxyacetate-zinc-aluminium-layered double hydroxide nanocomposite: physico-chemical and controlled release properties.

Layered organic-inorganic hybrid nanocomposite material was synthesised using 4-chlorophenoxyacetate (4CPA) as guest anion intercalated into the Zn-Al layered double hydroxide inorganic host by direct co-precipitation method at pH = 7.5 and Zn to Al molar ratio of 4. Both PXRD and FTIR results confirmed that the 4CPA was successfully intercalated into the Zn-AI-LDH interlayer. As a result, a well-ordered nanolayered organic-inorganic hybrid nanocomposite, with the expansion of the basal spacing from 8.9 angstroms in the layered double hydroxide to 20.1 angstroms in the resulting nanocomposite was observed. The FTIR spectrum of the nanocomposite (ZAC) showed that it composed spectral features of Zn-AI-LDH (ZAL) and 4CPA. The nanocomposites synthesized in this work are of mesoporous-type containing 39.8% (w/w) of 4CPA with mole fraction of Al3+ in the inorganic brucite-like layers (xAI) of 0.224. The release studies showed a rapid release of the 4CPA for the first 600 min, and more sustained thereafter. The total amount of 4CPA released from the nanocomposite interlayer into the aqueous solution were 21%, 66%, and 72% in 0.0001, 0.00025, and 0.0005 M sodium carbonate, respectively. In distilled water, about 75, 35, and 57% of 4CPA could be released in 1000 min, when the pH of the release media was set at 3, 6.25, and 12, respectively. In comparison with a structurally similar organic moiety with one more chlorine atom at the 2-position of the aromatic ring, namely 2,4-dichlorophenoxyacetate (24D), the 4CPA showed a slower release rate. The slightly bulkier organic moiety of 24D together with the presence of chlorine atom at the 2-position presumably had contributed to its higher release rate, and it seems that these factors may be exploited for tuning the release rate of intercalated guest anions with similar properties. This study suggests that layered double hydroxide can be used as a carrier for an active agent and the chemical structure of the intercalated moiety can be used to tune the desired release kinetics of the beneficial agent.