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    ACTIVATED NATURAL ZEOLITE

    ON TEXTILES FOR PROTECTIONAND THERAPY

    ACTIVATED NATURAL ZEOLITE

    ON TEXTILES FOR PROTECTIONAND THERAPY

    Ana Marija GRANCARI1, Anita TARBUK1,

    Slavko IVKOVI2, Tihomir LELAS3, Darko UJEVI1

    Ana Marija GRANCARI1, Anita TARBUK1,

    Slavko IVKOVI2, Tihomir LELAS3, Darko UJEVI1

    1 University of Zagreb, Faculty of Textile Technology,Zagreb, Croatia

    2

    Clinic Svecnjak Zagreb, Croatia3 Tribomin, Osijek, Croatia

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    INTRODUCTIONINTRODUCTION

    Human skin

    Is a barrier organIs the greatest human immune organIs a sensory organProtects againstCold,Heat,UV-R,

    Mechanical impact,Microorganisms.

    The purpose of finishing with zeolite nanoparticles is

    achieving high level multifunctionality of textiles.

    Human skin

    Is a barrier organIs the greatest human immune organIs a sensory organProtects againstCold,Heat,UV-R,

    Mechanical impact,Microorganisms.

    The purpose of finishing with zeolite nanoparticles is

    achieving high level multifunctionality of textiles.

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    Material name Natural Zeolite

    Chemical name Hydrated aluminosilicate from alkalis and earthalkalis

    Chemical type Molecular sieve

    Empirical formula (Ca, K2, Na2, Mg)4Al8Si40O96x 24 H2O

    Adsorption

    capacity

    Ammonia NH3,

    Hydrocarbons C1to C6Carbon dioxide CO2Hydrogen sulphide H2SSulphur dioxide SO2, nitrogen oxides NOX,aldehydes

    Total exchangecapacity Cations (Ca2+

    , K+

    , Na+

    , Mg2+

    )(1,2-1,5 mol / kg)

    ZEOLITE (CLINOPTILOLITE)ZEOLITE (CLINOPTILOLITE)

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    Substance Percentage

    SiO2 65,0 71,3 %

    Al2O3 11,5 13,1 %

    CaO 2,7 5,2 %

    K2O 2,2 3,4 %

    Fe2O3 0,7 1,9%

    MgO 0,6 1,2 %

    Na2O 0,2 1,3 %

    TiO2 0,1 0,3 %

    Si/Al ratio 4,8 5,4

    ZEOLITE (CLINOPTILOLITE)ZEOLITE (CLINOPTILOLITE)

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    Non-toxicEuropean approval as a food additive in

    accordance with DIN 53 770

    U.S. approval: Code of Federal Regulations,Food and Drugs (FDA), 21 CFR CH. I, 182Subpart C

    Non-toxicEuropean approval as a food additive in

    accordance with DIN 53 770

    U.S. approval: Code of Federal Regulations,Food and Drugs (FDA), 21 CFR CH. I, 182Subpart C

    ZEOLITE (CLINOPTILOLITE)ZEOLITE (CLINOPTILOLITE)

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    Clinoptilolite has a cage-like structure consistingof high portion of SiO2(60-67 %).

    ZEOLITE (CLINOPTILOLITE)ZEOLITE (CLINOPTILOLITE)

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    Zeolite - activated micronized particles ofclinoptilolite produced by tribomechanicalprocessing in the patented machine.

    Zeolite - activated micronized particles ofclinoptilolite produced by tribomechanicalprocessing in the patented machine.

    Such product has 80% of nanoparticles.Such product has 80% of nanoparticles.

    ZEOLITE (CLINOPTILOLITE)ZEOLITE (CLINOPTILOLITE)

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    TRIBOMECHANICAL ACTIVATIONTRIBOMECHANICAL ACTIVATION

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    TRIBOMECHANICAL ACTIVATIONTRIBOMECHANICAL ACTIVATION

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    LHC Large Hadron ColliderTRIBOMECHANICAL ACTIVATIONTRIBOMECHANICAL ACTIVATION

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    Stages of micronisingStages of micronising

    1. Particles

    are accelerated 2. Particles collide3. Particles rebound -

    surface friction

    4. Dynamics cause

    pulverising

    5. Dynamic process

    continues

    6. Crystal structure

    fragments

    TRIBOMECHANICAL ACTIVATIONTRIBOMECHANICAL ACTIVATION

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    Tribomechanical activation (TMA) is a newly

    developed micronizing method for improvingreaction capacity levels

    Special equipment is required: TMA disintegrator

    After processing, significant changes to theparticles can be observed with regard tosizesurface characteristicselectrostatic chargeion exchange capacity

    Tribomechanical activation (TMA) is a newly

    developed micronizing method for improvingreaction capacity levels

    Special equipment is required: TMA disintegrator

    After processing, significant changes to theparticles can be observed with regard tosizesurface characteristicselectrostatic chargeion exchange capacity

    MICRONIZINGMICRONIZING

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    is non-toxichas 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

    is non-toxichas 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

    EFFECTS OF ACTIVATED ZEOLITEEFFECTS OF ACTIVATED ZEOLITE

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    Megagreen

    Natural manure which improves photosynthetic activityMegagreen

    Natural manure which improves photosynthetic activity

    Photos: Crop trials with Megagreen in Lombardy, June 2004Photos: Crop trials with Megagreen in Lombardy, June 2004

    Untreated crops Crops treated with Megagreen

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    Scatter UV ligth

    UV PotectionGreat absorbens

    AntimicrobialProtection

    Scatter UV ligth

    UV PotectionGreat absorbens

    AntimicrobialProtection

    ACTIVATED NATURAL ZEOLITEON PROTECTIVE TEXTILES

    ACTIVATED NATURAL ZEOLITEON PROTECTIVE TEXTILES

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    MATERIAL and TREATMENTSMATERIAL and TREATMENTSLabel Treatment

    S

    Scoured (bioscouring with 1% Beisol PRO, Bezema) cotton

    knitted/woven fabricSM Scoured mercerized (24% NaOH) cotton fabrics

    SZ Scoured cotton fabrics, impregnated with 5 g/l zeolite

    nanoparticles

    SZM Scoured cotton fabrics, 5 g/l zeolite nanoparticles added in

    mercerization process

    SMZ Scoured mercerized cotton fabrics, impregnated with 5 g/l of

    zeolite nanoparticles

    SM(AZ) Scoured mercerized cotton fabrics, 5 g/l of zeolite nanoparticlesand azalide treated by exhaustion method

    ...A Azalide treated by exhaustion method

    ...W Washed according to ISO 105-C08/C09 using ECE Test Detergentwithout phosphate and without OBA

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    AZALIDE (AZI)AZALIDE (AZI)Azalides are subclass of macrolide antibiotics(macrocyclic lactone ring in their chemical structure).Azithromycin is the most famous azalide with brandnames Zithromax (Pfizer) and Sumamed (Pliva).

    Azalides are subclass of macrolide antibiotics(macrocyclic lactone ring in their chemical structure).Azithromycin is the most famous azalide with brandnames Zithromax (Pfizer) and Sumamed (Pliva).

    Azytromicine 9-deoxy-9a-aza-9a-methyl-

    9a-homoerythromycin A

    Azytromicine 9-deoxy-9a-aza-9a-methyl-

    9a-homoerythromycin A

    It is derived from erythromycin(14-membered lactone ring)

    by adding a nitrogen atom intothe lactone ring making

    15-membered lactone ring.

    It is derived from erythromycin(14-membered lactone ring)

    by adding a nitrogen atom intothe lactone ring making

    15-membered lactone ring.

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    SEM images ofzeolite treatedbioscouredcotton fabrics

    SEM images ofzeolite treatedbioscouredcotton fabrics

    SMZSMZ

    SZMSZM

    Images taken in DTNW,Krefeld, Germany

    a) during (SMZ) andb) after (SZM)mercerization process

    a) during (SMZ) andb) after (SZM)mercerization process

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    Characteristic Standard Instrument

    UV Protection

    ****UV ProtectionFactor (UPF)

    AS/NZS 4399:1996Sun ProtectiveClothing: evaluation

    and classification

    Transmission

    Spectrophoto-meter Cary 50Solarscreen(Varian)

    METHODSMETHODS

    indicates the ability of fabrics toprotect the skin against sun burning indicates how much longer a person

    can stay in the sun with the fabriccovering the skin as compared with

    the uncovered skin to obtain sameerythemal response

    S() = spectral irradiation [W m-2 nm-1]() = spectral transmittance = wavelength measuring interval [nm]

    SE

    SEUPF

    where: E() = spectral weighting

    function of erythemal actionspectra according to CIEJ.6;17-22.1989

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    Characteristic Standard Microorganisms used

    Antimicrobialactivity

    AATCC TM 147-1999Antibacterial Activity Assessment

    of Textile Materials

    andAATCC TM 100-1999

    Antibacterial Finishes on Textile

    Materials: Assesment of

    Gram positiveStaphylococcus aureus

    and

    Gram negative

    Klebsiella pneumoniae

    METHODSMETHODS

    In Petri dish (80 mm diameter) microorganisms were put. In the middle of dishcircle test sample, d = 24 mm, was placed. After incubation of 24 h diameter ofsample and diameter of influenced area were measured. Diameter difference

    quantitatively determines fabric protection of Gram positive and Gramnegative microorganisms.

    Results are given as factor, f

    In Petri dish (80 mm diameter) microorganisms were put. In the middle of dishcircle test sample, d = 24 mm, was placed. After incubation of 24 h diameter ofsample and diameter of influenced area were measured. Diameter difference

    quantitatively determines fabric protection of Gram positive and Gramnegative microorganisms.

    Results are given as factor, f

    untreated

    treated

    d

    df

    untreated

    treated

    d

    df

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    c)

    great antimicrobialactivity to

    Gram negativeKlebsiella

    pneumoniae

    b)

    great antimicrobialactivity to

    Gram positiveStaphylococus

    aureus

    a)

    noantimicrobial

    activity

    ANTIMICROBIAL PROTECTIONANTIMICROBIAL PROTECTION

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    Gram positiveStaphylococus aureus

    Gram positiveStaphylococus aureus

    0

    12

    24

    36

    48

    60

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA

    SMZ

    SMZA

    SM(AZ)

    d

    [mm]

    Treated

    Treated and washed

    Knitted cotton fabric

    Woven cotton fabric

    0

    12

    24

    36

    48

    60

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA

    SMZ

    SMZA

    SM(AZ)

    d

    [mm]

    Treated

    Treated and washed

    ANTIMICROBIAL PROTECTIONANTIMICROBIAL PROTECTION

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    Gram negativeKlebsiella pneumoniae

    Gram negativeKlebsiella pneumoniae

    Woven cotton fabric

    ANTIMICROBIAL PROTECTIONANTIMICROBIAL PROTECTION

    0

    12

    24

    36

    48

    60

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA

    SMZ

    SMZA

    SM(AZ)

    d

    [mm]

    Treated

    Treated and washed

    Knitted cotton fabric

    0

    12

    24

    36

    48

    60

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA

    SMZ

    SMZA

    SM(AZ)

    d

    [mm]

    Treated

    Treated and washed

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    Woven cotton fabric

    UV PROTECTIONUV PROTECTION

    0

    200

    400

    600

    800

    1000

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA

    SMZ

    SMZA

    SM(AZ)

    MeanUPF

    Treated

    Treated + washed

    Knitted cotton fabric

    0

    200

    400

    600

    800

    1000

    S SA SM SMA SZ SZ

    ASZ

    MSZ

    MA SMZ

    SMZA

    SM(AZ)

    Mea

    nUPF

    Treated

    Treated + washed

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    Activated natural zeolite

    modulates the immune system. Taking Megamin

    strengthens the bodys 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 bemeasured and is proven to exist

    Activated natural zeolite

    modulates the immune system. Taking Megamin

    strengthens the bodys 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 bemeasured and is proven to exist

    ACTIVATED NATURAL ZEOLITEFOR THERAPY

    ACTIVATED NATURAL ZEOLITEFOR THERAPY

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    absorbs gastric acid (during heartburn)

    regulates the pH values of human tissue

    (counteracting hyperacidity) is a remarkable prebiotic (bacterial activity in the

    intestine)

    influences cellular metabolism and throughmitochondrial activity also influences cell vitality

    is the best possible antioxidant. It neutralises and

    captures free radicals. is also an enzymatic antioxidant (high silicon

    ratio)

    absorbs gastric acid (during heartburn)

    regulates the pH values of human tissue

    (counteracting hyperacidity) is a remarkable prebiotic (bacterial activity in the

    intestine)

    influences cellular metabolism and throughmitochondrial activity also influences cell vitality

    is the best possible antioxidant. It neutralises and

    captures free radicals. is also an enzymatic antioxidant (high silicon

    ratio)

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    detoxifies our bodiesdetoxifies our bodies

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    possesses a highion exchangecapacity (potassium,

    sodium, magnesiumand calciumexchange)

    adsorbs andabsorbs ammoniain the enteron andcolon

    absorbs heavymetals (includinglead, arsenic,cadmium)

    possesses a highion exchangecapacity (potassium,

    sodium, magnesiumand calciumexchange)

    adsorbs andabsorbs ammoniain the enteron andcolon

    absorbs heavymetals (includinglead, arsenic,cadmium)

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    EFFECTS OF ACTIVATED ZEOLITEEFFECTS OF ACTIVATED ZEOLITE

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    Very strong antioxidative properties affect oxidativestress in cancer and diabetes patients. Additionally,diabetes mell itus patients can use zeolite for thereason of its glucose high absorbance.

    Free radicals are the main factors of manypathological changes in organisms.

    Total Antioxidant Status (TAS) measures theconcentration of antioxidants in the organisms. Frommany results it is shown that activated zeoliteinfluenced an increase in TAS value more than 26%which is in comparison to known antioxidants (A, C,and E vitamines, flaovoinouds, melatonin etc.) tenthtime effective.

    Very strong antioxidative properties affect oxidativestress in cancer and diabetes patients. Additionally,diabetes mell itus patients can use zeolite for thereason of its glucose high absorbance.

    Free radicals are the main factors of manypathological changes in organisms.

    Total Antioxidant Status (TAS) measures theconcentration of antioxidants in the organisms. Frommany results it is shown that activated zeoliteinfluenced an increase in TAS value more than 26%which is in comparison to known antioxidants (A, C,and E vitamines, flaovoinouds, melatonin etc.) tenthtime effective.

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    Anticancer activity of zeolite as antioxidants may notonly be attributed to their radical scavengerproperties, but also to direct modulation of cellular

    signal transduction pathways, resulting in growtharrest and apoptosis of cancer cells.

    Recently, it has been shown that 4 weeks of oral

    supplementation with activated zeolite resulted inrestoration of previously increased antioxidant levels(Randox Total Antioxidant Status) and decreases offree radicals (d-ROM-s Free Radical Analytical System)

    in plasma of cancer patients.

    Anticancer activity of zeolite as antioxidants may notonly be attributed to their radical scavengerproperties, but also to direct modulation of cellular

    signal transduction pathways, resulting in growtharrest and apoptosis of cancer cells.

    Recently, it has been shown that 4 weeks of oral

    supplementation with activated zeolite resulted inrestoration of previously increased antioxidant levels(Randox Total Antioxidant Status) and decreases offree radicals (d-ROM-s Free Radical Analytical System)

    in plasma of cancer patients.

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    Beside its antioxidant capacity, activated zeolitedemonstrated anticancer activity in vitro tissuecultures by inhibition of protein kinase B (c-Act) andinduction of expression of tumor suppressor proteins,independently from p53 protein. Blockade of cellgrowth has been shown in several cancer cell lines.The high inhibitory effects of zeolite are obtained withtwo cell lines, HeLa and MiaPaCa-2 what confirmed therecently results about zeolite inhibition of proteinkinase B (c-Act).

    Additionally, the combination of activated zeolite withdoxorubicin for the treatment of mammary carcinoma-bearing mice was significantly more effective inreducing the number pulmonary metastases whencompared to doxorubicin mono-therapy.

    Beside its antioxidant capacity, activated zeolitedemonstrated anticancer activity in vitro tissuecultures by inhibition of protein kinase B (c-Act) andinduction of expression of tumor suppressor proteins,independently from p53 protein. Blockade of cellgrowth has been shown in several cancer cell lines.The high inhibitory effects of zeolite are obtained withtwo cell lines, HeLa and MiaPaCa-2 what confirmed therecently results about zeolite inhibition of proteinkinase B (c-Act).

    Additionally, the combination of activated zeolite withdoxorubicin for the treatment of mammary carcinoma-bearing mice was significantly more effective inreducing the number pulmonary metastases whencompared to doxorubicin mono-therapy.

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    The effect of activated zeolite treatment (differentTMAZ concentration) on growth of different humancell lines.

    Legend:

    HeLa - cervical carcinoma; MiaPaCa-2 - pancreatic carcinoma;

    CaCo-2 - colon carcinoma; MCF-7 - breast cancer;

    Hep-2 - laryngeal carcinoma.

    The effect of activated zeolite treatment (differentTMAZ concentration) on growth of different humancell lines.

    Legend:

    HeLa - cervical carcinoma; MiaPaCa-2 - pancreatic carcinoma;

    CaCo-2 - colon carcinoma; MCF-7 - breast cancer;

    Hep-2 - laryngeal carcinoma.

    0

    30

    60

    90

    120

    150

    HeLa MiaPaCa-2 CaCo-2 MCF-7 Hep-2

    Cell lines

    Cellviabi

    lity[%]

    control0.05 mg/ml

    0.25 mg/ml0.5 mg/ml

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    In the wound healing are five importantrequirements: moist environment, antimicrobial,non-toxic to human cells, hypoallergenic andcontinuous debridement. Activated zeolite justfollows these requirements having favorableeffects on the healing of next superficial skin

    wounds:Acute skin problems -mechanical skin damage,

    thermal burns, abrasions, insect bites, post-operative wound treatment, herpes simplex andherpes zoster.Chronic skin problems- various skin infections,

    allergic reaction, degenerative diseases,neurodermitis, ulcer cruris, decubitus ulcers,etc.

    In the wound healing are five importantrequirements: moist environment, antimicrobial,non-toxic to human cells, hypoallergenic andcontinuous debridement. Activated zeolite justfollows these requirements having favorableeffects on the healing of next superficial skin

    wounds:Acute skin problems -mechanical skin damage,

    thermal burns, abrasions, insect bites, post-operative wound treatment, herpes simplex andherpes zoster.Chronic skin problems- various skin infections,

    allergic reaction, degenerative diseases,neurodermitis, ulcer cruris, decubitus ulcers,etc.

    Activated Natural Zeolite in Healing WoundsActivated Natural Zeolite in Healing Wounds

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    Activated natural zeolite: adsorbs sweat and stops unpleasant odors cleans the skin from oxidants and free radicals protects the body against harmful UV radiation

    regardless of the fabric structure, applyingtreatment, or washing processUV protection in textile finishing meansantioxidative protection, as well.

    protects the body from microorganisms and preventsits access and activity

    has favorable effects on the healing process in theskin wounds

    CONCLUSIONCONCLUSION

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    Activated natural zeolite:

    constantly holds the body temperatureincrease energy levels of entire bodyprotects of rheumatic problemsenhances exchanges of substances in the body and

    helps the skin breathregulates the pH values of skin andis very comfortable to wear.

    Tribomechanical activated natural zeolite on textilespromises multifunctional properties and differentbiological effects in the near future what requires further

    research work.

    CONCLUSIONCONCLUSION

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    ACTIVATED NATURAL ZEOLITE ONTEXTILES FOR PROTECTION AND

    THERAPY

    ACTIVATED NATURAL ZEOLITE ONTEXTILES FOR PROTECTION AND

    THERAPY

    Ana Marija GRANCARI1, Anita TARBUK1,

    Slavko IVKOVI2, Tihomir LELAS3, Darko UJEVI1

    Ana Marija GRANCARI1, Anita TARBUK1,

    Slavko IVKOVI2, Tihomir LELAS3, Darko UJEVI1