METAL COMPLEXES OF MACROCYCLES AND/OR ISOPRENOIDS AND/OR LINEAR TETRAPYRROLES BY MECHANOCHEMISTRY (GRINDING OR MILLING), PREPARATION METHOD THEREOF, SUNSCREEN/CONCEALER/UV ABSORBER THEREOF, SELF-ASSEMBLED COATING MATERIAL THEREOF, SUPERAMPHIPHILIC MATERIAL OR SURFACES THEREOF, HAIR DYEING THEREOF AND OTHER USES THEREOF

摘要

Metal complexes of macrocycles and/or isoprenoids and/or linear tetrapyrroles by mecha nochemistry (grinding or milling), preparation method thereof, sunscreen/concealer/UV absorber thereof, self- assembled coating material thereof, superamphiphilic material or surfaces thereof, hair dyeing thereof and other uses thereof. Converting biomass, including products from its own process-line wastes, into high value products such as biofuel, bioplastics and biochemicals in an attempt to replace oil consumption has become nowadays a challenge for innovation. In one embodiment of the present invention, a novel product obtained from the solvent-free mechanochemical reaction (grinding and milling) of biomass and a metal alkoxide is produced. In one embodiment of the present invention, Spirulina biomass, comprising macrocycles (chlorophyll) and isoprenoids (P-carotene) and linear tetrapyrroles (phycobilins attached to proteins), is ground or milled together with a metal alkoxide to produce a stable colored material. If a monomer or polymer is added to the mechanochemical reaction, another kind of colored composite material with different or enhanced properties is produced. The present invention relates to a method to synthesize with high yield a colored metal complex of macrocycles and/or isoprenoids and/or linear tetrapyrroles by mecha nochemistry under solvent-free conditions and covers new complexes obtained therefrom. In an embodiment, only the reactants, a metal alkoxide and a macrocycle and/or an isoprenoid and/or a linear tetrapyrrole, are present and react at different molar ratios to form a metal complex in the form of a homogeneous colored material (e.g. powder) with high yield and stability. If a macrocycle phthalocyanine is used, the color of the final metal complex dye depends on several factors such as the metal, the type of alkoxide used, the stoichiometric molar ratio of both reactants and the additives used. If titanium alkoxide with or without additives is used, a blue colored titanium macrocycle complex in any form (e.g. powder form) is produced. The production process of the metal complex in powder form is characterized by facility of scale up. The entire product is ready to be used in several applications. If other macrocycle compounds (e.g. porphyrins and calixarenes) and/or isoprenoids (e.g. p-carotenoids or squalene) and/or linear tetra pyrroles (e.g. phycocyanin or bilirubin) are used instead of only phthalocyanine, other complexes of different colors are obtained using mechanochemistry. In addition, the product comprising metal complexes of macrocycles and/or isoprenoids and/or linear tetrapyrroles is characterized by green chemistry manufacture. Besides, these metal complexes of macrocycles and/ or isoprenoids and/or linear tetrapyrroles in several formulations are characterized by improved stability under storage conditions, improved flocculation stability and improved sun protection against UV rays for human skin and human hair. The product is ready to be used alone or in combination with other additives (e.g. titanium oxide) or active ingredients in different formulations. The invention also covers the use of these metal macrocycle/isoprenoid/linear tetrapyrrole complexes in food, cosmetics, the pharmaceutical field and in the creativity field, as sunscreen, skin and hair concealer or foundation in powder form or cream, keratinous dye, textile dye, food dye, dye emulsions, miniemulsions, polymer colloids, catalysts (e.g. light harvesting complex for artificial photosynthesis) and coatings. The production process of these metal-complex dyes of the present invention is also characterized by rapid production of colored compounds without using solvents and, thus, ecofriendliness. The process of the production of metal macrocycle and/or isoprenoid/ terpenoid and/or linear tetrapyrrole complexes is characterized by the non-formation of toxic by-products and high yield. In addition, the present invention comprises a hair dyeing molecule or formulation and procedure combining excellent dyeing properties with reduced risk of development of cancer or allergies, while being ecological and of natural origin and with a broad spectral range of colors. In other aspect of the present invention, a physical mixture, comprising macrocycles and/or isoprenoids and/or linear tetrapyrroles, is ground and milled together with a titanium alkoxide to produce a black colored material similar to black pigments obtained from non-renewable resources. Besides, the new macrocycles in a metallo-supramolecular system display new properties such as superamphiphilicity that enhance self- assembly film formation with further uses in several applications, such as biosensors, drug delivery, photonic/electronic devices, light harvesting devices.