Effect of confinement of anionic organic ultraviolet ray absorbers into two-dimensional zinc hydroxide nitrate galleries

Abstract

Espécies aniônicas absorvedoras de radiação ultravioleta (UV) (4-metoxibenzoato, N-acetilantranilato, 4-metoxicinamato e 4,4'-diamino-2,2'-estilbenodissulfonato) foram intercaladas em hidroxinitrato de zinco pelo método de co-precipitação ou reação de troca aniônica topotática. A intercalação foi confirmada por difratometria de raios X de pó (XRPD), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), análise térmica (TGA/DTA), microscopia eletrônica de varredura (SEM), difração de elétrons em área selecionada (SAED), análise elementar e espectroscopia eletrônica na região do ultravioleta-visível (UV-Vis). Na reação de co-precipitação uma intercalação completa foi observada, enquanto na reação de troca aniônica os íons nitrato só foram parcialmente substituídos pelos ânions orgânicos. Após a intercalação, a capacidade de absorção de radiação UV foi similar à dos sais e ácidos sólidos, sendo o efeito atribuído ao confinamento das espécies aniônicas na galeria bidimensional da matriz hospedeira. Essa observação abre novas oportunidades para o uso de matrizes lamelares alternativas para a imobilização de ânions, na formulação de protetores solares.Anionic ultraviolet (UV) ray absorbers (4-methoxybenzoate, N-acetylanthranilate, 4-methoxycinnamate and 4,4'-diamino-2,2'-stilbenedisulfonate) were intercalated into zinc hydroxide nitrate, either by direct alkaline co-precipitation or topotactic exchange reactions. The intercalation was confirmed by X-ray powder diffractometry (XRPD), Fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA/DTA), scanning electron microscopy (SEM), selected area electron diffraction (SAED), elemental analysis and ultraviolet visible (UV-Vis) spectroscopy. In the co-precipitation reactions full intercalation was achieved, while during the exchange reactions nitrate anions were not completely replaced by the organic anions. After the intercalation, the UV absorption capacity was similar to that of the solid salts and acids, the effect being attributed to the confinement of the anionic species in the host two-dimensional gallery. This observation opens new opportunities for the use of organic anions immobilized in alternative layered matrixes for the formulation of sunscreens.Keywords: zinc hydroxide nitrate, UV ray absorbers, sunscreens, layered materials, intercalation IntroductionHealth problems related to the exposure to solar ultraviolet (UV) radiation can be minimized by the use of sunscreens and other cosmetic filters. These products are regularly used by millions around the globe. Because of their frequent and long-term use, special attention has been devoted to the efficiency and safety of these formulations. 1UV ray absorbing organic molecules are widely employed as active ingredients of sunscreens. Among such substances are anthranilates and cinnamates.2 Although there are a large number of anthranilates (also known as ortho-aminobenzoates), only two of them are commonly found in commercial products: homomethyl-N-acetylEffect of Confinement o...

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