BRPI1003893A2 - solubilising composition of inorganic and organic samples of animal, plant and human origin - Google Patents

Abstract

Solubilising Composition of Inorganic and Organic Samples of Animal, Vegetable and Human Origin The present invention describes a composition comprising benzyltrimethylammonium hydroxide or alkoxide - BzTMAH - in water, in methanol, in ethanol, unrestricted in any proportion - and preferably peroxide hydrogen peroxide - at any concentration for alkaline solubilization of inorganic and organic samples of animal, vegetable and human origin, effluent and waste, food, beverages, hygiene and cleaning products, cosmetics, petrochemicals of non-limiting sugarcane, seeds and biodiesel products. The use of this solubilizing composition has been shown to be safe, fast, simple, easy, efficient and reproducible by promoting solubilization instantaneously or within 48 hours, with or without agitation, in a temperature range between 0 <198> and 120 <198> C. and without the use of any acid digestion system, or by microwave or ultrasound irradiation (although these systems accelerate and increase the efficiency and speed of solubilization even more). Even in the most insoluble samples after two nights at rest (or using microwave or ultrasound) solubilization was complete.

Description

"SOLUBILIZING COMPOSITION OF INORGANIC AND ORGANIC SAMPLES OF VEGETABLE AND HUMAN ANIMAL ORIGIN"

FIELD OF INVENTION

The present invention describes a composition comprising benzyltrimethylammonium hydroxide or alkoxide - BzTMAH - in water, methanol, ethanol, in any proportion - and peroxide, preferably hydrogen peroxide - at any concentration for alkaline solubilization of inorganic samples and organic sources of animal, plant and human origin, effluents and waste, food, beverages, hygiene and cleaning products, cosmetics, petrochemicals, sucrochemistry, seeds and biodiesel products, not limiting.

The use of this solubilizing composition has been shown to be safe, fast, simple, easy, efficient and reproducible by promoting solubilization instantaneously or within 48 hours, with or without agitation, in a temperature range between 0 ° C and 120 ° C and without any use. acid digestion system, or by microwave or ultrasound irradiation (although these systems accelerate and increase the efficiency and speed of solubilization even more). Even in the most insoluble samples after two nights at rest (or using microwave or ultrasound) solubilization was complete. Sample preparation for chemical component analysis

Organic and inorganic substances of any biological material is a key and critical point in establishing the appropriate analytical methodology [E.C. Lima, F. Barbosa, F.J. Krug, M.M. Silva, M.G.R. Vale, J. Anal. Atom Spectrom. 15, 995 (2000); S. Souza, D. Santos, F.J. Krug, F. Barbosa, Talanta 73, 451 (2007); B.J. Bolann, R. Rahil-Khazen, H. Henriksen, R. Isrenn, R.J. Uluik, J. Scand, Clin. Lab. Invest. 67, 353 (2007); E.C. Lima, F. Barbosa, F.J. Krug, Anal. Chim. Acta 409, 267 (2000); R. Bock, A Handbook of Decomposition Methods in Analytical Chemistry, International Textbook Company, London 1979; Zeculcek, P. Povondra, Methods of Decomposition in Inorganic Analysis, CRC Press, Boca Raton, 1989; M. Stoeppler (Ed.); Sampling and Sample Preparation. Practical Guide for Analytical Chemists, Springer, Berlin, 1997; C. Vandecasteele1 C.B. Block1 Modern Methods for Trace Element Determination, John Wiley & Sons, Chichester1 1993],

Several advances in sample preparation have been achieved in recent decades, with emphasis on the sample opening procedure using microwave assisted heating [H.M. (Skip) Kingston, L.B. Jassie (Ed.), Introduction to Microwave Sample Preparation. Theory and Practice American Chemical Society Washington, 1988; H.M. (Skip) Kingston, S.J. Haswell (Ed.). Microwave-Enhaneed Chemistry. Fundamentals, Sample Preparation, and Applications, American Chemical Society, Washington, 1997; Z. Mester, R.E. Sturgeon (Ed.). Sample Preparation for Trace EIementAnaIysis, Elsevier, Amsterdam, 2003; M. Hoenig, A.-M. from Kersabiec, Sample preparation steps for analysis by atomic spectroscopy methods: present status, Spectrochim. Acta Part B 51, 1297 (1996); K.S. Subramanian, Determination of metals in biofluids and tissues: sample preparation methods for atomic spectroscopic techniques, Spectrochim. Acta Part B 51, 291 (1996); FAITH. Smith, E.A. Arsenault, Microwave-assisted sample preparation in analytical chemistry, Talanta 43, 1207 (1996); M. Burguera, J.L. Burguera, Microwave-assisted sample decomposition in flow analysis, Anal. Chim. Acta 366, 63 (1998); M. Hoenig, Preparation Steps in Environmental Trace Element Analysis, Talanta 54, 1021 (2001)].

The use of alkaline reagents in methods known today as alkaline solubilization, for example the use of tetramethylammonium hydroxide (TMAH) 1 from water soluble tertiary amines (CFA-C) and other strong bases for sample preparation, has greatly called researchers' attention in several articles [B. L. Batista, J.L. Rodrigues, J.A. Nunes, L.Tormen, A.J. Curtius, F. Barbosa Jr., Talanta 76 (2008) 575] and with the focus of general knowledge having been centered on an important recent review article [J. A. Nobrega, M.C. Santos, R.A. de Sousa, S.Cadore, R.M. Barnes, M.Tatro1 Spectrochimica Aeta Part B 61, 465 (2006)]. Tetramethylammonium hydroxide (TMAH) - (CH3) 4N + (OH) "- is a base

not well known even in the area of chemistry and has become more common in the area of analytical chemistry because of its use in alkaline solubilization methodologies of biological samples. However, in the area of Organic Chemistry we know the benzyl analog of TMAH, benzyltrimethylammonium hydroxide - C6H5CH2 (CH3) 3N + (OH) "- or BzTMAH which is a stronger base and more solubility in most solvents [Fieser and Fieser's, Reagents for Organic Synthesis, John Wiley and Sons, Inc., USA, v.1, p.1252, 1967; v.11, p.514, 1984] being most commonly used in certain specific organic reactions. BzTMAH has been frequently studied and important literature has been found [CLDonnici, B.WIadislaw, L. Marzorati, T. T. Pereira, JOF Melo Synthetic Communications 28, 4179 (1998); Chaturvedi, D; Mishra, Chaturvedi, AK; ibid, 39, 1273 (2009); Li, Z; Marler, B.; Gies, H.; Chemistry of Materials 20, 1896 (2008); Chiang Y; Kresge, AJ; Zhu, Y; Journal of the American Chemical Society, 123, 8089 (2001); Sata, T.; Tsujimoto, M.; Yamaguchi, T.; Journal of Membrane Science, 112, 161 (1996). associated with processes of

patenting the use of BzTMAH associated with synthetic methods and various industrial processes, but there are no patenting processes in place for the use of BzTMAH as an alkaline solubilizing agent. Among those found in the state of the art, the following can be highlighted: JP2551298-B2 discloses the use of BzTMAH in the key step of

synthesis of naphthyloxazolidonic derivatives;

JP3041999-B2 discloses the use of BzTMAH for obtaining (S) -1-para-methoxybenzyloxy-2,3-epoxypropane;

JP61036276-A reports the use of BzTMAH for the synthesis of 1,3-dioxolan-2-one derivatives;

EP24503-A1 describes the occurrence of N-denitration of N, 2,6-trinitrile anilines by the use of BzTMAH;

CN101328153-A shows the use of BzTMAH in the preparation of tris (phenoxy tribromo) triazine. JP94035449-B2 report the use of BzTMAH for the preparation of phthalazine derivatives;

EP206298-B1, reports that ethylene cyanhydrin and analogous functionalized ethers can be prepared by the use of BzTMAH; US4209643-A shows the use of BzTMAH in the preparation of acetals from olefins and hydroformylation reaction;

US3928343-A describes obtaining isocyanurates such as 1,3-bis (2-carboxyethyl) -5-phenyl isocyanurate with the use of BzTMAH;

US3833661-A reports the production of tris (hydroxymethyl) phosphine

using BzTMAH;

EP0361334-B1, shows the use of BzTMAH to obtain flexible polyurethanes;

US4769505-A also describes the use of BzTMAH in the preparation of (2,2) -paracyclophane using co-solvents and reaction promoters;

Patent Application BR8802300-A also reports the obtaining of paracyclophan using BzTMAH;

CA867255-A reports that the dimensional stability of cellulose textiles is enhanced by condensing agents such as BzTMAH;

KR2008029412-A reports that BzTMAH, TMAH and other analogous bases can be used for cleaning semiconductor substrates, as well as US6551973 discloses the use of BzTMAH for the removal of polymeric organic substances;

US7157213-B2 reports that TMAH, BzTMAH and other bases can be used to efficiently and quickly treat photosensitive substrates;

US3706691-A discloses that BzTMAH can be used as a solvent in encapsulating compounds;

JP3035166 (A) describes a reagent method for preventing turbidity in a biological sample;

US20090884509 (A1) discloses a method for dissolving cellulose, wherein one of the components of the solubilizing mixture is BzTMAH.

30 DESCRIPTION OF THE INVENTION

The present invention describes a composition for alkaline solubilization of organic samples of animal, plant and human origin, microorganisms, food, beverages, cosmetics, pharmaceuticals, hygiene and cleaning products, effluents, waste, petrochemical, seed and biodiesel and soil products, not limited by the use of benzyltrimethylammonium hydroxide or alkoxide, BzTMAH - dissolved in water, methanol, ethanol, or any other unrestricted solvent - in any proportion and peroxide - preferably hydrogen peroxide - at any concentration, or any unrestricted solvent, as a solubilizing agent. The concentration to be used for complete solubilization depends on the sample characteristics.

Solubilization occurs with any animal tissue (skin, tissues, nails, hair, hair, hair, organs, bones) or plant tissue (trunks, flowers, leaves, twigs, roots) and with any mineral and inorganic samples (coordination compounds and organometallic compounds). , catalysts) or biological (mushrooms, insects, micro-organisms) and biological residues (urine, faeces, blood and blood and organ residues) and any other organic, animal and plant samples, namely: meat and meat (cattle, pigs , horses, goats, poultry, fish, crustaceans, oysters, octopuses, squids and any other animals) and miscellaneous foods such as: eggs (of any animals, both fresh and yolk and egg whites), soy (powdered, common or flavored beverages with soymilk), breast milk, milk (powdered and common) and various dairy products (miscellaneous cheeses such as cream cheese, even grated cream cheese and the hardest cheese; yogurt from natural and flavored to fruit), coffee (powder, grains, soluble and granulated), teas (mate, black, mint, fennel and any other), beverages (soft drinks of any kind, energy drinks, various alcoholic beverages: cachaça, beer, whiskey, vodka, sake, martini, campari and others; white and red wines, sparkling wines, soft drinks and juices (natural or artificial, powdered, granulated and liquid), sugar (common, crystal and diced) and honey (of all kinds and brands), biscuits (sweet and savory, and stuffed, wheat or sprinkles), crackers (sweet and salty of all kinds), toast and bread, candies, gum and gummies and confectionery of various kinds, pasta and flour (wheat, sprinkles, oatmeal, cornstarch, rye, hops and baking powder, semi-ready-made cake, pies and pastry mixes, smoked mixes (cold cuts of various kinds, such as hams, salami, roast beef, mortadella and others) and other canned goods (tuna and sardines or other fish, sausages and other meat products), pates, mayonnaise, catchups, mustards and other seasonings, jellies and jellies (powder or leaf), chocolates (bar, powder and cream), margarines and butter as, lard, cooking oils (olive oil, soybean, canola, corn, sunflower), eucalyptus, copaiba, andiroba oils and other natural oils) and agricultural products in general such as tubers and vegetables (carrots, chayote, cassava) , common potatoes, sweet potatoes), cereals (rice (common or parboiled), Brazilian or Italian ("carnaroli"), raw or cooked), beans (white, black or brown of any kind, raw or cooked), chickpeas, lentils, puff pastry and miscellaneous vegetables (lettuce, kale, cauliflower, watercress, arugula, basil, broccoli, parsley, chives, almond, taioba), fresh fruits (banana, kiwi, orange, tangerine, grapes , peach, pineapple, mango, melon, watermelon, strawberry, olive), dried fruits (walnuts, hazelnuts, almonds, Brazil nuts and cashews, apricots, raisins, peanuts), seeds (sunflower, flaxseed, birdseed, walnut). nutmeg), common and dried seasonings (garlic, leeks, onions, basil, bay leaves, oregano, paprika, herbal spices) f various colors. The solubilizing composition also dissolves cosmetic samples (lipstick, eyeshadow, pencil, nail polish, face powder, foundation, eyeliner, oils, suntan lotions, creams and lotions), cleansers (liquid or paste detergents, washing powder, paste soap , stone soap, bleach and miscellaneous cleaning products) and hygiene (soaps, shampoos, after-wash and combing creams, thermal or otherwise, cream or roll-on deodorants), products from petrochemical sources ( crude oil, diesel oil, naphtha, gasoline, greases and lubricating oils and even coke), sugar products (sugarcane, sugarcane bagasse, syrup, molasses, filter cake, sugar, brown sugar, ethanol), biodiesel products, sources or residues (biodiesel oil producing seeds, seed residues and extraction pies, extracted oils and crude and purified biodiesel). Various pharmaceutical formulations (in liquid form, tablets, powders, capsules, globules, syrups, gels, creams and lotions) are also rapidly dissolved by the solubilizing agent as well as various soil samples.

Sample opening procedures using:

• microwave assisted heating is usually too long to be established as routine methods with

number of samples for analysis, as well as requiring the use of concentrated acids and very careful monitoring of digestion [F. Barbosa, I. Ramires, M.H.C. Rodrigues, T.D. SainfiPierre, A.J. Curtius, M.R. Buzalaf, R.F. Gerlach, J.E. Tanus-Santos, Environ. Res. 102, 90 (2006)]

• alkaline reagents, for example the use of tetramethylammonium hydroxide (TMAH), water soluble tertiary amines (CFA-C) and other strong bases, solubilization can only be achieved at long time and with heating.

With the proposed methodology, which is fast and efficient, it is possible to

also, easily preparing suitable samples for analysis of appreciable group of inorganic analytes (at varying concentration levels to trace levels) - selected from the group comprising Ag, Al, As, Au, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cu, Cr, Cs, Fe, Ga, Ge, Hf, Hg, In, Go, K, Li, Mg, Mn, Mo, Os, On, Nb, Ni, Pb, Pd, Po, Pt, Ra, Rb, Re, Rh, Ru, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tc, Te, Ti, Ti, V, W, Zn, Zr, Y, U and all actinide elements and lanthanides by the most varied spectrometric techniques - and organic analytes - such as residues of any analyzable organic compounds such as pesticides, drugs, hormones, enzymes, proteins by various chromatographic and spectrometric techniques, such as liquid and gas chromatography (GC / GC). and conventional two-dimensional HPLC / HPLC (CGxCG / GCxGC), conventional ionization (MS / MS) and electrospray (MS / MS-ESI) mass spectrometry.

Alkaline solubilization, in another aspect, performed on different types of samples facilitates and increases the analysis with precision and acuity, highlighting that the resulting solutions are clear and transparent, with no residue or precipitate occurring, in most cases, making Solubilized samples compatible with inorganic and organic compounds analysis by the usual techniques mentioned above.

It is important to highlight that by developing a simpler and more suitable methodology for sample preparation, acid digestions, extractions and other problems for the use of chemical analysis spectrometric techniques are avoided, making them more viable for large sample analysis.

The proposed methodology can be better understood with the following non-limiting example:

EXAMPLE

The alkaline solubilization experiment is performed by adding 1 ml of the solubilizing composition to 100 mg of the material to be solubilized in a 15 ml conical tube. Solubilization may be immediate or after a maximum of 48 hours with magnetic, mechanical, or vortexing within a temperature range of 0 ° C to 120 ° C. For more insoluble samples, total solubilization can be achieved with microwave or ultrasound irradiation. The sample obtained may be neutralized by treatment and dilution with up to 10 ml of 1% (v / v) aqueous nitric acid solution or acetic acid for the performance of analytical experiments by ET-AAS or ICP-MS / OES for analysis of the studied metals and - with or without SPE / SPME treatment or extraction with acetonitrile and cooling - by CG-MS or ESI-MS for analysis of organic components.

Table 1 reports the results obtained in solubilizing various types of samples using the solubilizing composition of the present invention compared to tetramethylammonium hydroxide (TMAH). Table 1- Results of solubilization of various sample types using the solubilizing composition of the present invention compared to tetramethylammonium hydroxide (TMAH).

Samples Solubilizing composition TMAH Fruits and leaves: Kiwi, peach, strawberry, mango, pineapple, guava, orange, apple, papaya, kale and lettuce Complete solubilization of fruit pulps. Does not solubilize kiwi and guava seeds. Little leaf residue left Low solubilization. Much residues of intact shell, pulp and seeds Meat and eggs: egg yolk, egg white, salmon, ham, beef, beef liver, tomato sardines and tuna Complete solubilization Does not completely solubilize. Phases have been formed (egg yolk, egg white, ham) and others are left with residues and or gelatinous (salmon, sardines, tuna) Oils and fats: olive oil, vegetable margarine and butter Complete solubilization of olive oil and low solubilization margarine Complete solubilization of olive oil. Does not solubilize margarine and butter solution has solidified after some time. Sugars: honey, candy, brown sugar, plum jam and brown sugar. Complete solubilization. Partial solubilization. Chocolate bar. Complete solubilization but with creamy consistency. and mozzarella), yogurt, milk Complete solubilization Does not completely solubilize. After solubilization the solution in powder, whole milk and pasteurized skimmed solidified (cheese) or phase division (milk) Cosmetics: lipstick, eyeshadow, nail polish, face powder, pencil and foundation Solubilizes completely (lipstick, eyeshadow, foundation) Does not solubilize Oil and derivatives: petroleum, gasoline, petrochemical naphtha, coke and diesel oil Complete solubilization (petrol, diesel, naphtha and petroleum) Incomplete solubilization (petrol, diesel, naphtha and petroleum) Seeds: granulated coffee, flaxseed, olive, raw beans and rice raw Complete solubilization, except for incomplete olives Does not solubilize or is poorly solubilized with many residues (coffee) Cereals, roots, tubers and derivatives: wheat flour, cassava flour and cornmeal, wheat biscuit, sprinkle biscuit, pasta , oats and potatoes Complete solubilization, but the solution becomes gelatinous Does not solubilize

Claims (8)

1.- SOLUBILIZING COMPOSITION, characterized in that it comprises a solution of benzyltrimethylammonium hydroxide or alkoxide and peroxide. 2. A solubilising composition according to claim 1, characterized in that the components: benzyltrimethylammonium hydroxide or alkoxide and peroxide are previously dissolved, isolated or not in a solvent and then added to a sample; or by directly adding the composition to a sample without solvent. Solubilising composition according to claims 1 and 2, characterized in that the peroxide is preferably hydrogen peroxide. 4. A solubilising composition according to any one of claims 1 to 3, characterized in that the solvent used in the dissolution of benzyltrimethylammonium hydroxide or alkoxide and / or peroxide is selected from the group comprising: water, methanol, ethanol, A7-propanol, iso- propanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, cyclohexanol, octanol, acetone, ethyl acetate, butyl acetate, acetonitrile, tetrahydrofuran, diethyl ether, dimethyl sulfoxide, N, N-dimethylformamide, Ν , Β-dimethylacetamide, dichloromethane, chloroform or nitrobenzene in any proportion. 5. A solubilising composition according to any one of claims 1 to 4, characterized in that it is added to the sample in a temperature range between 0 ° C and 120 ° C, with immediate solubilization or for up to 48 hours under stirring or no, with or without microwave irradiation, with or without sonication ultrasound. 6.- SOLUBILIZING COMPOSITION, characterized by being used in the solubilization of samples from inorganic and organic sources selected from the group comprising plants, animals, human, biological and microbiological, biochemical residues, residues and effluents from industrial, domestic or hospital environmental, beverages, food. , seeds, edible oils and natural oils, micro-organisms, cosmetics and pharmaceuticals (in liquid, powder, tablet, globule, capsule, syrup, gel, paste, cream and lotion form), hygiene or cleaning products, products or wastes from petrochemical sources, petrochemicals products, biodiesel products and residues (biodiesel oil producing seeds, seed residues and extraction pies, extracted oils and crude and purified biodiesel) and soils. 7.- SOLUBILIZING COMPOSITION, characterized in that it is used in the preparation of samples for analysis of any metals, selected from the group comprising Ag, Al, As, Au, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cu, Cr, Cs, Fe, Ga, Ge, Hf, Hg, In, Ir, K, Li, Mg, Mn, Mo, Os, Nb, Ni, Pb, Pd, Po, Pt, Ra, Rb, Re, Rh, Ru, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tc, Te, Ti, TI, V, W, Zn, Zr, Y, U and all other actinide and lanthanide elements. 8.- SOLUBILIZING COMPOSITION, characterized in that it is used in the preparation of samples for analysis of organic components, selected from the group comprising residues (industrial, domestic and hospital), pesticides, plastics, surfactants, food additives, drugs, dyes, pigments and compounds. technological, industrial or scientific use and of biochemical interest (hormones, enzymes and proteins).