Nanoparticles of Activated Natural Zeolite on Textiles for Protection and Therapy

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1 Nanoparticles of Activated Natural Zeolite on Textiles for Protection and Therapy Ana Marija GRANCARIĆ 1, Anita TARBUK 1, Ivančica KOVAČEK 2 1 University of Zagreb, Faculty of Textile Technology, Zagreb, Croatia 2 Zagreb Institute of Public Health, Zagreb, Croatia INTRODUCTION Human skin Is a barrier organ Is the greatest human immune organ Is a sensory organ Protects against Cold, Heat, UV-R, Mechanical impact, Microorganisms. The purpose of finishing with zeolite nanoparticles is achieving high level multifunctionality of textiles. 1

2 ZEOLITE (CLINOPTILOLITE) Material name Chemical name Chemical type Empirical formula Adsorption capacity Total exchange capacity Natural Zeolite Hydrated aluminosilicate from alkalis and earth alkalis Molecular sieve (Ca, K 2, Na 2, Mg) 4 Al 8 Si 40 O 96 x 24 H 2 O Ammonia NH 3, Hydrocarbons C 1 to C 6 Carbon dioxide CO 2 Hydrogen sulphide H 2 S Sulphur dioxide SO 2, nitrogen oxides NOX, aldehydes Cations (Ca 2+, K +, Na +, Mg 2+ ) (1,2-1,5 mol / kg) ZEOLITE (CLINOPTILOLITE) Non-toxic European approval as a food additive in accordance with DIN U.S. approval: Code of Federal Regulations, Food and Drugs (FDA), 21 CFR CH. I, 182 Subpart C 2

3 ZEOLITE (CLINOPTILOLITE) Clinoptilolite has a cage-like structure consisting of high portion of SiO 2 (60-67 %). ZEOLITE (CLINOPTILOLITE) Substance Percentage SiO 2 65,0 71,3 % Al 2 O 3 11,5 13,1 % CaO 2,7 5,2 % K 2 O 2,2 3,4 % Fe 2 O 3 0,7 1,9% MgO 0,6 1,2 % Na 2 O 0,2 1,3 % TiO 2 0,1 0,3 % Si/Al ratio 4,8 5,4 3

4 ZEOLITE (CLINOPTILOLITE) Zeolite - activated micronized particles of clinoptilolite produced by tribomechanical processing in the patented machine. Such product has 80 % of nanoparticles. Tribomechanical activation 4

5 Tribomechanical activation Tribomechanical activation Stages of micronising 1. Particles are accelerated 2. Particles collide 3. Particles rebound - surface friction 4. Dynamics cause pulverising 5. Dynamic process continues 6. Crystal structure fragments 5

6 Tribomechanical activation Tribomechanical activation (TMA) is a newly developed micronizing method for improving reaction capacity levels Special equipment is required: TMA After processing, significant changes to the particles can be observed with regard to size surface characteristics electrostatic charge ion exchange capacity EFFECTS OF ACTIVATED ZEOLITE is non-toxic has neither chemical or pharmacological effects has only a biophysical effect This biophysical effect is used to regulate growth, cell division and differentiation (protection and repair mechanisms) is used in agicultural, industrial and medical purposes 6

Taking Megamin strengthens the body s immune system is a carrier of energy and information is a product developed with new technology

7 Megagreen Natural manure which improves photosynthetic activity Photos: Crop trials with Megagreen in Lombardy, June 2004 Untreated crops Crops treated with Megagreen ZEOLITE FOR THERAPY Activated natural zeolite modulates the immune system. Taking Megamin strengthens the body s immune system is a carrier of energy and information is a product developed with new technology which enhances an existing biophysical effect. This enhanced biophysical effect can be measured and is proven to exist absorbs gastric acid (during heartburn) 7

ZEOLITE FOR THERAPY regulates the ph values of human tissue (counteracting hyperacidity) is a remarkable prebiotic (bacterial activity in the intestine) influences cellular metabolism and through

8 ZEOLITE FOR THERAPY regulates the ph values of human tissue (counteracting hyperacidity) is a remarkable prebiotic (bacterial activity in the intestine) influences cellular metabolism and through mitochondrial activity also influences cell vitality is the best possible antioxidant. It neutralises and captures free radicals. is also an enzymatic antioxidant (high silicon ratio) ZEOLITE FOR THERAPY detoxifies our bodies 8

and absorbs ammonia in the enteron and colon absorbs heavy

9 ZEOLITE FOR THERAPY possesses a high ion exchange capacity (potassium, sodium, magnesium and calcium exchange) adsorbs and absorbs ammonia in the enteron and colon absorbs heavy metals (including lead, arsenic, cadmium) ZEOLITE FOR THERAPY 9

10 ZEOLITE FOR THERAPY Very strong antioxidative properties affect oxidative stress in cancer and diabetes patients. Additionally, diabetes mellitus patients can use zeolite for the reason of its glucose high absorbance. Free radicals are the main factors of many pathological changes in organisms. Total Antioxidant Status (TAS) measures the concentration of antioxidants in the organisms. From many results it is shown that activated zeolite influenced an increase in TAS value more than 26% which is in comparison to known antioxidants (A, C, and E vitamines, flaovoinouds, melatonin etc.) tenth time effective. ZEOLITE FOR THERAPY Anticancer activity of zeolite as antioxidants may not only be attributed to their radical scavenger properties, but also to direct modulation of cellular signal transduction pathways, resulting in growth arrest and apoptosis of cancer cells. Recently, it has been shown that 4 weeks of oral supplementation with activated zeolite resulted in restoration of previously increased antioxidant levels (Randox Total Antioxidant Status) and decreases of free radicals (d-rom-s Free Radical Analytical System) in plasma of cancer patients. 10

11 ZEOLITE FOR THERAPY Activated zeolite demonstrated anticancer activity in vitro tissue cultures by inhibition of protein kinase B (c-act) and induction of expression of tumor suppressor proteins, independently from p53 protein. Blockade of cell growth has been shown in several cancer cell lines. The high inhibitory effects of zeolite are obtained with two cell lines, HeLa and MiaPaCa-2 what confirmed the recently results about zeolite inhibition of protein kinase B (c-act). Additionally, the combination of activated zeolite with doxorubicin for the treatment of mammary carcinomabearing mice was significantly more effective in reducing the number pulmonary metastases when compared to doxorubicin mono-therapy. ZEOLITE FOR THERAPY The effect of activated zeolite treatment (different TMAZ concentration) on growth of different human cell lines. Cell viability [%] control 0.05 mg/ml 0.25 mg/ml 0.5 mg/ml Legend: HeLa - cervical carcinoma; MiaPaCa-2 - pancreatic carcinoma; CaCo-2 - colon carcinoma; MCF-7 - breast cancer; Hep-2 - laryngeal carcinoma. 0 HeLa MiaPaCa-2 CaCo-2 MCF-7 Hep-2 Cell lines 11

ZEOLITE IN HEALING WOUNDS In the wound healing are five important requirements: moist environment, antimicrobial, non-toxic to human cells, hypoallergenic and continuous debridement.

12 ZEOLITE IN HEALING WOUNDS In the wound healing are five important requirements: moist environment, antimicrobial, non-toxic to human cells, hypoallergenic and continuous debridement. Activated zeolite just follows these requirements having favorable effects on the healing of next superficial skin wounds: Acute skin problems - mechanical skin damage, thermal burns, abrasions, insect bites, postoperative wound treatment, herpes simplex and herpes zoster. Chronic skin problems - various skin infections, allergic reaction, degenerative diseases, neurodermitis, ulcer cruris, decubitus ulcers, etc. ZEOLITE ON PROTECTIVE TEXTILES Scatter UV ligth UV Potection Great absorbens Antimicrobial Protection 12

METHODS Characteristic Standard Instrument UV Protection **** UV Protection Factor (UPF) UPF = ΣE AS/NZS 4399:1996 Sun Protective Clothing: evaluation and classification ΣE( λ ) S( λ ) λ ( λ) S( λ )

13 METHODS Characteristic Standard Instrument UV Protection **** UV Protection Factor (UPF) UPF = ΣE AS/NZS 4399:1996 Sun Protective Clothing: evaluation and classification ΣE( λ ) S( λ ) λ ( λ) S( λ ) τ ( λ ) λ where: E(λ) = spectral weighting function of erythemal action spectra according to CIE J.6; S(λ) = spectral irradiation [W m -2 nm -1 ] τ(λ) = spectral transmittance λ = wavelength measuring interval [nm] Transmission Spectrophotometer Cary 50 Solarscreen (Varian) indicates the ability of fabrics to protect the skin against sun burning indicates how much longer a person can stay in the sun with the fabric covering the skin as compared with the uncovered skin to obtain same erythemal response METHODS Characteristic Standard Microorganisms used Antimicrobial activity EN ISO Textile fabrics -Determination of antibacterial activity - Agar diffusion plate test Gram positive Staphylococcus aureus and Gram negative Klebsiella pneumoniae In Petri dish (80 mm diameter) microorganisms were put. In the middle of dish circle test sample, d = 24 mm, was placed. After incubation of 24 h diameter of sample and diameter of influenced area were measured. Diameter difference quantitatively determines fabric protection of Gram positive and Gram negative microorganisms. d D = d treated untreated [ mm] 13

ZEOLITE ON TEXTILES Material and Treatments for COTTON Label CB CBM CBZ CBZM CBMZ CBM(AZ).

bleached cotton fabrics, impregnated with 5 g/l zeolite nanoparticles bleached cotton fabrics, 5 g/l zeolite

zeolite nanoparticles bleached mercerized cotton fabrics, 5 g/l of zeolite nanoparticles and azalide treated by

14 ZEOLITE ON TEXTILES Material and Treatments for COTTON Label CB CBM CBZ CBZM CBMZ CBM(AZ)...A Treatment bleached with H 2 O 2 cotton knitted/woven fabric bleached mercerized (24% NaOH) cotton fabrics bleached cotton fabrics, impregnated with 5 g/l zeolite nanoparticles bleached cotton fabrics, 5 g/l zeolite nanoparticles added in mercerization process bleached mercerized cotton fabrics, impregnated with 5 g/l of zeolite nanoparticles bleached mercerized cotton fabrics, 5 g/l of zeolite nanoparticles and azalide treated by exhaustion method azalide treated by exhaustion method SEM - Cotton B BMZ BM BZM Zeolite implemented during (BMZ) after (BZM) mercerization process 14

15 UV PROTECTION Mean UPF Fabric Fabric+FWA CB CBM CBZ CBMZ AZALIDE (AZI) Azalides are subclass of macrolide antibiotics (macrocyclic lactone ring in their chemical structure). Azithromycin is the most famous azalide with brand names Zithromax (Pfizer) and Sumamed (Pliva). It is derived from erythromycin (14-membered lactone ring) by adding a nitrogen atom into the lactone ring making 15-membered lactone ring. Azytromicine 9-deoxy-9a-aza-9a-methyl- 9a-homoerythromycin A 15

ANTIMICROBIAL PROTECTION a) no antimicrobial activity b) great antimicrobial

activity to Gram negative Klebsiella pneumoniae ANTIMICROBIAL PROTECTION

activity CB 24 no 24 no CBA 42 high 30 high CBM 24 no 24 no CBMA 44,5 high

16 ANTIMICROBIAL PROTECTION a) no antimicrobial activity b) great antimicrobial activity to Gram positive Staphylococus aureus c) great antimicrobial activity to Gram negative Klebsiella pneumoniae ANTIMICROBIAL PROTECTION Sample Staphylococus aureus Klebsiella pneumoniae D [mm] activity D [mm] activity CB 24 no 24 no CBA 42 high 30 high CBM 24 no 24 no CBMA 44,5 high 39,5 high CBZ 25 small 24 no CBZA 42 high 37 high CBMZ 34,5 high 29 small CBMZA 48 high 42 high 16

17 ZEOLITE ON TEXTILES Material and Treatments for POLYESTER Label PET PETH PETZ PETHZ Treatment Untreated polyester fabric Hydrolized polyester fabric in 1,5 mol/l naoh Polyester fabric impregnated with 5 g/l zeolite Hydrolized polyester fabric impregnated with 5 g/l zeolite SEM - Polyester PET PET-Z PETH PETH-Z 17

18 UV PROTECTION Mean UPF Fabric Fabric+FWA PET PETH PETZ PETHZ CONCLUSION Activated natural zeolite: adsorbs sweat and stops unpleasant odors cleans the skin from oxidants and free radicals has favorable effects on the healing process in the skin wounds constantly holds the body temperature increase energy levels of entire body protects of rheumatic problems enhances exchanges of substances in the body and helps the skin breath regulates the ph values of skin and is very comfortable to wear. 18

CONCLUSION Activated natural zeolite applied on textile : contribute to UV protection by scattering UV radiation and show synergism with FWA s what leads to excellent for cotton and very good UV

19 CONCLUSION Activated natural zeolite applied on textile : contribute to UV protection by scattering UV radiation and show synergism with FWA s what leads to excellent for cotton and very good UV protection for polyester. added to azalides in textile finishing, increase the efficiency of antimicrobial action to both - Gram positive as well as Gram negative bacteria. Textile and clothing with activated zeolite can protect the skin from microbes and UV radiation, showing effects on the healing process in the skin wounds and therapy effect against different shin diseases like, psoriasis, cancer etc. Nanoparticles of Activated Natural Zeolite on Textiles for Protection and Therapy Ana Marija GRANCARIĆ Anita TARBUK Ivančica KOVAČEK amgranca@ttf.hr 19

Available on line at Association of the Chemical Engineers AChE

Available on line at Association of the Chemical Engineers AChE ANA MARIJA GRANCARIĆ 1 ANITA TARBUK 1 IVANČICA KOVAČEK 2 1 Faculty of Textile Technology, University of Zagreb, Croatia 2 Zagreb Institute of Public Health, Zagreb, Croatia REVIEW PAPER Zeolites are hydrated