WE PROPOSE THE SYNTHESIS OF ?-TRIKETONATE COMPLEXES OF ZN(II) AND CU(II) AS PRECURSORS IN THE PHOTO-DEPOSITION OF ZNO FILMS LOADED WITH CUO, WHICH ARE SUBSEQUENTLY CALCINED AT 600 ?C. THE ZNO/CUO HETEROJUNCTION SYSTEM WAS ANALYZED BY XRD, SEM AND XPS; THE RESULTS DEMONSTRATE LOW CRYSTALLINITY OF THE FILMS AND THE FORMATION OF ZNO AND CUO. THE RESULTS OF OPTICAL PROPERTIES CONFIRM A GRADUAL REDUCTION OF THE OPTICAL BANDGAP WHEN CUO LOADING IS INCREASED IN THE ZNO MATRIX AND THE PHOTOLUMINESCENCE TESTS FOUND A DECREASE IN THE EMISSION BANDS OF THE ZNO MATRIX WITH THE INSERTION OF CUO. THE MAXIMUM PHOTO-DEGRADATION EFFICIENCY IS ACHIEVED FOR ZNO FILMS LOADED WITH CUO AT 1 MOL%, OBTAINING 75.4 AND 68.3% FOR RHODAMINE B AND RHODAMINE 6G, RESPECTIVELY. WE PROPOSE THAT ZNO IS RESPONSIBLE FOR THE FORMATION OF SUPEROXIDE RADICALS AS THE MAIN REACTIVE SPECIES IN THE DEGRADATION OF BOTH RHODAMINES.

ZNAL2O4 AND MGAL2O4 THIN FILMS WERE GROWN ON SI(100) AND QUARTZ PLATE SUBSTRATES USING A PHOTOCHEMICAL METHOD IN THE SOLID PHASE WITH THIN FILMS OF BETA-DIKETONATE COMPLEXES AS THE PRECURSORS. THE FILMS WERE DEPOSITED BY SPIN-COATING AND SUBSEQUENTLY PHOTOLYZED AT ROOM TEMPERATURE USING 254 NM UV LIGHT. THE PHOTOLYSIS OF THESE FILMS RESULTS IN THE DEPOSITION OF METAL OXIDE THIN FILMS AND FRAGMENTATION OF THE LIGANDS FROM THE COORDINATION SPHERE OF THE COMPLEXES. THE OBTAINED SAMPLES WERE POST-ANNEALED AT DIFFERENT TEMPERATURES (350?1100 °C) FOR 2 H AND CHARACTERIZED BY FT-INFRARED SPECTROSCOPY, X-RAY DIFFRACTION (XRD), X-RAY PHOTOELECTRON SPECTROSCOPY (XPS), ATOMIC FORCE MISCROSCOPY (AFM), AND UV?VIS SPECTROSCOPY. THE RESULTS INDICATE THE FORMATION OF SPINEL-TYPE STRUCTURES AND OTHER PHASES. THESE CHARACTERISTICS DETERMINED THE QUALITY OF THE FILMS, WHICH WERE OBTAINED FROM THE PHOTODEPOSITION OF TERNARY METAL OXIDES.

IN THIS STUDY, WE EVALUATED THE PHOTOCATALYTIC EFFICACY OF PURE Y2TI2O7 FILMS INCORPORATING VARYING AGO RATIOS (1.0, 3.0, AND 5.0 MOL%) IN THE DEGRADATION PROCESS OF BRILLIANT GREEN DYE AND IN THE BACTERIAL DISINFECTION OF ESCHERICHIA COLI UNDER UV?VISIBLE ILLUMINATION. THE FILMS WERE PREPARED UTILIZING A PHOTOCHEMICAL METHODOLOGY INVOLVING ?-DIKETONATE COMPLEXES OF Y(DBM)3, TI(DBM)4, AND AG(ACAC) AS STARTING MATERIALS. FOLLOWING SYNTHESIS, THE PHOTO-DEPOSITS UNDERWENT CALCINATION AT 900 °C FOR 2 H AND WERE SUBSEQUENTLY ANALYZED USING FOURIER TRANSFORM INFRARED SPECTROSCOPY, X-RAY DIFFRACTION, SCANNING ELECTRON MICROSCOPY - ENERGY DISPERSIVE X-RAY SPECTROSCOPY, AND X-RAY PHOTOELECTRON SPECTROSCOPY. THE OUTCOMES OF THESE CHARACTERIZATIONS INDICATE THE FORMATION OF A PYROCHLORE Y2TI2O7 CUBIC PHASE, WITH THE EMERGENCE OF AGO IN THE DOPED SAMPLES. PHOTOCATALYTIC PERFORMANCE YIELDED SIGNIFICANT RESULTS, WITH A 94.9 % DEGRADATION OF BRILLIANT GREEN OBSERVED FOR Y2TI2O7 SAMPLES DOPED AT 3.0 MOL%, AND A 98.4 % INHIBITION OF ESCHERICHIA COLI CULTURES OBSERVED FOR Y2TI2O7 SAMPLES DOPED AT 1.0 MOL%. THEORETICAL CALCULATIONS WERE EMPLOYED TO DETERMINE THE BAND EDGE POTENTIALS OF BOTH OXIDES, SUPPORTING THE ESTABLISHMENT OF A TYPE I HETEROJUNCTION BETWEEN THE Y2TI2O7 PHASE AND AGO. A DEGRADATION MECHANISM HAS BEEN POSTULATED BASED ON ASSAYS INVOLVING THE BLOCKING OF REACTIVE OXYGEN SPECIES AND CHARGE CARRIERS THROUGH THE USE OF SPECIFIC

THIS PAPER PRESENTS A PHOTOCHEMICAL SYNTHESIS METHOD FOR PRODUCING PURE CEO2 DEPOSITS AND CEO2 DEPOSITS LOADED WITH VARYING PROPORTIONS OF FE2O3. THE DEPOSITS WERE CALCINED AT 950 °C AND CHARACTERIZED STRUCTURALLY, COMPOSITIONALLY, AND MORPHOLOGICALLY USING XRD, XPS, SEM, FT-IR, AND RAMAN SPECTROSCOPY TECHNIQUES. CERIANITE AND HEMATITE PHASES WERE IDENTIFIED IN CEO2/FE2O3 SAMPLES, INDICATING HETEROGENEOUS SURFACE DEPOSITS. PHOTOCATALYTIC TESTING UNDER UV?VIS ILLUMINATION FOR 5 H DEMONSTRATED PROMISING RESULTS. FOR THE DEGRADATION OF BRIGHT GREEN DYE, EFFICIENCIES OF 78.9 % AND 90.1 % WERE ACHIEVED FOR PURE CEO2 AND CEO2 SAMPLES LOADED WITH 1.0 MOL% FE2O3, RESPECTIVELY. SIMILARLY, FOR OXYTETRACYCLINE DRUG DEGRADATION, PERFORMANCE RATES OF 35.3 % AND 67.0 % WERE OBSERVED FOR CEO2 AND CEO2 SAMPLES LOADED WITH 1.0 MOL% FE2O3, RESPECTIVELY. RECYCLABILITY TESTS SHOWED A GRADUAL DECLINE IN PHOTOCATALYTIC PERFORMANCE OVER SUCCESSIVE CYCLES DUE TO BY-PRODUCT ACCUMULATION CONTAMINATING THE CATALYST.

THIS STUDY WAS CONDUCTED TO ASSESS THE CATALYTIC ELECTRODE SURFACE ADSORPTION AND CAPTURE PROPERTIES OF DIFFERENT METAL CHITOSAN DERIVATIVES IN AQUEOUS PHOSPHATE BUFFER SOLUTION (PH?=?7.3). EARLY, RECENT WORK SHOWED THAT THE RESPONSE OF IRON CHITOSAN COMPLEX WITH R?=?-CH3 ON THE PERIPHERY, OVER BLOOD RED CELLS IN PRESENCE OF SPHINGOMYELINASE C WAS PROTECTED. THE EFFECT OF OTHERS SUBSTITUENT (R?=?-BR, -CL, -F, NO2, -OCH3, -H) ON THE PERIPHERY OF THE SCHIFF BASE LIGAND DID NOT SHOW CORRELATION WITH THE OXIDATION OF SPHINGOMYELINASE C AND ITS BIOLOGICAL RESPONSE. FOR THIS REASON, VARIOUS ADSORBED METAL (M?=?FE OF RECENT WORK, CU, NI AND CO) COMPLEXES OF CHITOSAN AND SCHIFF BASES ON GLASSY CARBON ELECTRODE FOR THE OXIDATION OF SPHINGOMYELINASE C WERE INVESTIGATED AND COMPARED, EACH ONE WITH -CH3 GROUP ON THE PERIPHERY OF THE SCHIFF BASE. UV?VIS AND IR-TF SPECTROSCOPIES, ELECTROCHEMISTRY AND MICROSCOPY ASSAY WERE PERFORMED; THEN, THE METAL EFFECT UNDERLYING. FOR THE SCHIFF BASE, COBALT AND COPPER COMPLEXES DID NOT PROVED TO BE A REMARKABLE CELLULAR PROTECTOR IN PRESENCE OF THE ENZYME, BUT THE NICKEL COMPLEX SHOWED TO BE A CELLULAR PROTECTOR AT SHORT TIME, THIS CONCLUSION HELP TO PROPOSAL A REACTION MECHANISM FOR THE ELECTROCHEMICAL AND BIOLOGICAL STUDIES.

WE PROPOSE THE USE OF ALKOXIDE ?-DIKETONATES OF CE(III), ER(III), PR(III) AND YB(III) AS PRECURSORS FOR PHOTOCHEMICAL DEPOSITION OF CEO2:ER AND CEO2:ER/LN (LN = PR OR YB) THIN FILMS, FOLLOWED BY SUBSEQUENT ANNEALING AT 950 °C. THE MEASUREMENTS OF LUMINESCENT PROPERTIES REVEALED THAT CEO2:ER SAMPLES UNDER EXCITATION AT 980 NM EXHIBIT UP-CONVERSION EMISSIONS AT 540 NM AND NEAR INFRARED EMISSIONS CENTERED AT 1550 NM. WHEN CO-DOPING IS PERFORMED ON THE CEO2 FILMS, CEO2:ER/PR REDUCES ITS UP-CONVERSION CHARACTERISTICS AND THE NIR EMISSIONS INCREASE. HOWEVER, THE CEO2:ER/YB SAMPLES SIGNIFICANTLY INCREASE THE UP-CONVERSION PROPERTIES AND INHIBIT NIR EMISSIONS. DIFFERENT MECHANISMS BASED ON ENERGY TRANSFER PROCESSES ARE PROPOSED TO EXPLAIN THESE DIFFERENCES IN THE DEGREE OF INTENSITY OF THESE EMISSIONS.

THE REDOX POTENTIAL OF MACROCYCLIC COMPLEXES IS A VERY PREDICTIVE REACTIVITY INDEX FOR THE ELECTROCATALYTIC ACTIVITY OF THESE MOLECULES, AND IT CAN BE EASILY MEASURED UNDER THE SAME CONDITIONS OF THE CATALYSIS EXPERIMENTS. IT REFLECTS DIRECTLY THE ACTIVITY OF A GIVEN COMPLEX. WE HAVE INVESTIGATED THE EFFECT OF THE FE(II)/(I) FORMAL POTENTIAL ON THE CATALYTIC ACTIVITY OF A SERIES OF FE PORPHYRINS AND FE PHTHALOCYANINES FOR THE ELECTROOXIDATION OF L-CYSTEINE, WITH THE COMPLEXES DIRECTLY ADSORBED ON ORDINARY PYROLYTIC GRAPHITE OR ADSORBED ON MULTI-WALLED CARBON NANOTUBES (MWCNTS) DEPOSITED ON GRAPHITE. A CORRELATION OF LOG J (AT CONSTANT POTENTIAL) VERSUS THE FE(II)/(I) FORMAL POTENTIAL OF THE CATALYSTS GIVES A VOLCANO CURVE FOR BOTH SYSTEMS WITHOUT AND WITH MWCNTS WITH HIGHER ACTIVITIES IN THE LATTER CASE. OUR RESULTS CLEARLY SHOW THAT THE HIGHEST CATALYTIC ACTIVITY IS ACHIEVED IN A RATHER NARROW POTENTIAL WINDOW OF FE(II)/(I) FORMAL POTENTIALS OF N4-MACROCYCLIC COMPLEXES. THE USE OF MWCNTS AS SUPPORTING MATERIAL FOR THE CATALYSTS DOES NOT CHANGE THE REACTIVITY TRENDS OF THE FE COMPLEXES.

THE MEDICAL TREATMENT OF LAXOSCELISMS IS BASED SOLELY ON SUPPORTIVE MEASURES. ALTHOUGH EQUINE ANTISERUM FOR SPHINGOMYELINASE C (SMASE) AND D ISOMERS ARE AVAILABLE, IT IS NOT USED DUE TO THE RISK OF AN ANAPHYLACTIC REACTION AND ITS UNPROVEN EFFICACY. AS POTENTIAL ENZYME INHIBITORS, DERIVATIVES OF IRON CHITOSAN COMPLEXES WERE STUDIED (SHIFF BASE HAVING ?R = ?H, ?CL, ?BR, ?F, ?OCH3, ?CH3, ?NO2). THESE CHITOSAN COMPLEXES WERE CHOSEN BECAUSE THEY HAVE REVEALED GOOD RESULTS IN MEDICINE AND CATALYSIS DUE TO THEIR BIODEGRADABLE CHARACTERISTICS AND BIOAVAILABILITY. BESIDES CONSIDERING THAT THESE COMPLEXES HAVE NOT BEEN STUDIED IN RELATION TO THIS TOXIN. THE MECHANISMS UNDERLYING THE CATALYTIC AND CATCHER EFFECTS OF IRON CHITOSAN COMPLEXES WERE STUDIED USING ELECTROCHEMISTRY, UV?VIS SPECTROSCOPY AND MICROSCOPIC ASSAY AT PHYSIOLOGICAL PH. THE ELECTROCHEMICAL STUDIES SHOWED THAT ONE OF SEVEN SCHIFF BASES OF CHITOSAN ADSORBED ON GLASSY CARBON ELECTRODE WAS ELECTROCATALYTICALLY ACTIVE FOR THE OXIDATION OF SPHINGOMYELINASE AT 1.27 V, AND THAT ALLOWED PROPOSING A REACTION SCHEME FOR SMASE OXIDATION BY ADSORBED IRON COMPLEXES. ON THE OTHER HAND, EVEN THOUGH THE SPECTROSCOPIC STUDIES INDICATED THAT THERE WAS NO CHEMICAL BOND FORMATION BETWEEN THE COMPLEX AND SMASE IN SOLUTION, THE MICROSCOPIC STUDIES SHOWED THAT THIS COMPLEX PROVED TO BE A REMARKABLE CELLULAR PROTECTOR IN PRESENCE OF THE ENZYME. IN CONCLUSION, SHIFF BASE OF CHITOSAN WITH R = ?CH3 WAS THE ONLY ACTIVE COMPLEX IN FRONT OF SPHINGOMYELINASE C, PROTECTING RED BLOOD CELLS, ACCORDING TO OUR ELECTROCHEMICAL AND MICROSCOPIC STUDIES.

INHIBITION OF MELATONIN PRODUCTION DURING NIGHT HOURS INCREASES THE IMPAIRMENT OF METABOLISM, ELEVATING THE RISK OF OBESITY, HYPERGLYCEMIA, AND DYSLIPIDEMIA DURING PREGNANCY. FRUCTOSE CONSUMPTION HAS DETRIMENTAL EFFECTS OVER METABOLISM AND THE CIRCADIAN SYSTEM. SEVERAL REPORTS SUGGEST THAT MELATONIN HAS A PROTECTOR ROLE DURING THE PREGNANCY BY THEIR ANTIOXIDANT/CHRONOBIOTIC PROPERTIES, AND FROM THE ABOVE, WE SPECULATES TO MELATONIN CAN BE REVERTING THE CHRONODISRUPTION AND ELEVATION OF MASTER REGULATORS OF LIPID METABOLISM IN THE NEWBORN. MEASURE IN THE LIVER OF NEWBORN THE MRNA EXPRESSION OF CLOCK-GENE BMAL-1, HMG-COA REDUCTASE, SREBP AND THE CLOCK-CONTROLLED GENE WEE-1 OF THE NEWBORN FROM MOTHER TREATED WITH FRUCTOSE AND MELATONIN.

THE M(II)/(I) FORMAL POTENTIAL OF MN4 MACROCYCLIC COMPLEXES DICTATES THEIR ELECTROCATALYTIC ACTIVITY FOR MANY REACTIONS AND L-CYSTEINE OXIDATION IS NOT AN EXCEPTION. IN THIS WORK WE REVIEW THE LITERATURE RELATED TO THIS REACTION AND PROPOSE A SEMI-EMPIRICAL MODEL THAT CAN DESCRIBE THE CATALYTIC ACTIVITY OF THESE CHELATES IN TERMS OF THEIR FORMAL POTENTIAL. A CORRELATION OF LOG I (AT CONSTANT POTENTIAL) VERSUS THE M(II)/(I) FORMAL POTENTIAL FOR M= FE,CO) OF THE CATALYSTS GIVES A VOLCANO CURVE. OUR RESULTS CLEARLY SHOW THAT THE M (II)/(I) FORMAL POTENTIAL OF N4-MACROCYCLIC COMPLEXES NEEDS TO BE ADJUSTED TO VALUES AROUND -1.0 V VS. SCE TO OBTAIN THE HIGHEST CATALYTIC ACTIVITY FOR THE OXIDATION OF L-CYSTEINE. WHEN COMPARING CHELATES OF DIFFERENT METALS (M= CR, MN, FE, CO) OF TETRASULPHONATED PHTHALOCYANINES ONLY A LINEAR CORRELATION IS OBTAINED.

(BA, CA, SR)ZRO3?X THIN FILMS WERE PREPARED BY A PHOTOCHEMICAL METHOD USING THIN FILMS OF ?-DIKETONATE COMPLEXES AS PRECURSORS. THE PHOTOLYSIS OF THESE FILMS INDUCES THE FRAGMENTATION OF THE 2,2,6,6-TETRAMETHYL-3,5-HEPTANEDIONATE LIGAND AND THE PARTIAL REDUCTION OF METAL ION TOGETHER WITH VOLATILE ORGANIC COMPOUNDS AS SUB-PRODUCTS. WHEN THE METALLIC COMPLEXES ARE IRRADIATED IN AIR, THE FINAL PRODUCT OF THE REACTION ARE TERNARY METAL OXIDES. THE PHOTOREACTIVITY OF THESE FILMS WAS MONITORED BY FT-IR SPECTROSCOPY BY A PERIOD OF 72 H, FOLLOWED BY POST-ANNEALING AT 950 °C. X-RAY PHOTOELECTRON SPECTROSCOPY AND X-RAY DIFFRACTION TECHNIQUES WERE USED TO ANALYZE THE CHEMICAL COMPOSITION AND THE CRYSTALLINE STRUCTURE OF THE FILMS OBTAINED. THE RESULTS INDICATE THAT BA, CA, SR, ZR AND O ARE PRESENT IN THE FORM OF PEROVSKITA, PREFERABLY ADOPTING AN AMORPHOUS STRUCTURE. THE SURFACE MORPHOLOGY EXAMINED BY ATOMIC FORCE MICROSCOPY REVEALED A ROUGH AND IRREGULAR SURFACE. THE UV?VIS MEASUREMENTS SUGGEST A SLIGHT INCREASE IN THE OPTICAL BAND GAP VALUES, WHICH PROMOTE A REDUCTION OF THE INTERMEDIARY ENERGY LEVELS OR DEFECTS.

INCREASED CONSUMPTION OF ENERGY-DENSE FOODS SUCH AS FRUCTOSE-RICH SYRUPS REPRESENTS ONE OF THE SIGNIFICANT, GROWING CONCERNS RELATED TO THE ALARMING TREND OF OVERWEIGHT, OBESITY, AND METABOLIC DISORDERS WORLDWIDE. METABOLIC PATHWAYS AFFECTED BY FRUCTOSE INVOLVE GENES RELATED TO LIPOGENESIS/LIPOLYSIS, BETA-OXIDATION, MITOCHONDRIAL BIOGENESIS, GLUCONEOGENESIS, OXIDATIVE PHOSPHORYLATION PATHWAYS, OR ALTERING OF CIRCADIAN PRODUCTION OF INSULIN AND LEPTIN. MOREOVER, FRUCTOSE CAN BE A RISK FACTOR DURING PREGNANCY ELEVATING THE RISK OF PRETERM DELIVERY, HYPERTENSION, AND METABOLIC IMPAIRMENT OF THE MOTHER AND FETUS. MELATONIN IS A CHRONOBIOTIC AND HOMEOSTATIC HORMONE THAT CAN MODULATE THE HARMFUL EFFECTS OF FRUCTOSE VIA CLOCK GENE EXPRESSION AND METABOLIC PATHWAYS, MODULATING THE EXPRESSION OF PPAR?, SREBF-1 (SREBP-1), HORMONE-SENSITIVE LIPASE, C/EBP-? GENES, NRF-1, PGC1?, AND UNCOUPLING PROTEIN-1. MOREOVER, THIS HORMONE HAS THE CAPACITY IN THE RAT OF REVERTING THE HARMFUL EFFECTS OF FRUCTOSE, INCREASING THE BODY WEIGHT AND WEIGHT RATIO OF THE LIVER, AND INCREASING THE BODY WEIGHT AND RESTORING THE GLYCEMIA FROM MOTHERS EXPOSED TO FRUCTOSE. THE AIM OF THIS REVIEW IS TO SHOW THE POTENTIAL CROSSTALK BETWEEN FRUCTOSE AND MELATONIN AND THEIR POTENTIAL ROLE DURING PREGNANCY.

Y2O3 THIN FILMS DOPED WITH DIFFERENT CONCENTRATIONS OF ERBIUM IONS AND CO-DOPED WITH 10 MOL% OF YTTERBIUM WERE SYNTHESIZED BY A SOLID STATE PHOTOCHEMICAL DEPOSITION METHOD FOLLOWED BY A SUBSEQUENT CALCINATION PROCESS. THE PHOTO-REACTIVITY OF THE THIN FILMS WAS MONITORED BY FOURIER TRANSFORM INFRARED (FT-IR) SPECTROSCOPY. XRAY DIFFRACTION (XRD), X-RAY PHOTOELECTRON SPECTROSCOPY (XPS), SCANNING ELECTRON MICROSCOPY (SEM), UV-VIS SPECTROSCOPY AND PHOTO-LUMINESCENCE (PL) WERE EMPLOYED TO CHARACTERIZE THE SAMPLES. THE RESULTS REVEAL THAT Y2O3:ER FILMS UNDER 980 NM IRRADIATION EXHIBIT CHARACTERISTIC UP-CONVERSION EMISSIONS THAT ARE FOCUSED IN THE GREEN REGION OF THE SPECTRUM; THESE EMISSIONS ARE ASSIGNED TO THE (H-2(11/2), S-4(3/2)) -> I-4(15/2) TRANSITIONS OF THE ER3+ IONS. THESE EMISSIONS GREATLY INCREASE IN INTENSITY WITH THE ADDITION OF YB3+ IONS IN THE PREPARATION OF THE CODOPED FILMS. THIS PHENOMENON IS EXPLAINED BASED ON THE EFFICIENT YB3+ -> ER3+ ENERGY TRANSFER PROCESSES.

THIN FILMS OF ZRO2 LOADED WITH 10, 30 AND 50 MOL% SM WERE PREPARED BY A PHOTOCHEMICAL METHOD USING THIN FILMS OF METAL ACETYLACETONATE COMPLEXES AS PRECURSORS. THE PHOTOLYSIS OF THESE FILMS INDUCES THE FRAGMENTATION OF THE ACETYLACETONATE LIGAND AND THE PARTIAL REDUCTION OF METAL ION TOGETHER WITH VOLATILE ORGANIC COMPOUNDS. WHEN THE METALLIC COMPLEX IS EXPOSED TO AIR, THE PRODUCT OF THE REACTION IS METAL OXIDE. THE PHOTOREACTIVITY OF THESE FILMS WAS MONITORED BY FT-IR SPECTROSCOPY, FOLLOWED BY A POST-ANNEALING TREATMENT PROCESS. THE OBTAINED FILMS WERE CHARACTERIZED BY X-RAY PHOTOELECTRON SPECTROSCOPY AND ATOMIC FORCE MICROSCOPY.

THE CHITOSAN?(FE(II), CO(II), AND CU(II)) COMPLEXES WERE PREPARED BY MIXING CHITOSAN (CHI) POWDER WITH A SALICYLALDEHYDE (SAL, 5-HYDROGEN (?H)) AND THEIR 5-BROMO (?BR), 5-CHLORO (?CL), 5-METHOXY (?OCH3), 5-FLUORO (?F), 5-METHYL (?CH3), AND 5-NITRO (?NO2) DERIVATIVES (GROUPS R) AND MIXING THESE WITH FECL2 AND CUCL2 IN ETHANOL AND WITH CO(CH3COO)2 SOLUTIONS IN BUTANOL AT 80 °C OVER 8 H IN HETEROGENEOUS PHASE, FOLLOWED BY EXTRACTION WITH ETHANOL AND BUTANOL, RESPECTIVELY. THE COMPLEXES WERE CHARACTERIZED BY FTIR AND UV?VIS SPECTROSCOPY, ELEMENTAL ANALYSIS, AND CYCLIC VOLTAMMETRY. A LINEAR CORRELATION BETWEEN THE METAL FORMAL POTENTIAL VERSUS THE HAMMETT PARAMETERS OF THE SUBSTITUENTS WAS OBSERVED. THE ELECTRON-WITHDRAWING GROUPS SHIFT THE REDOX POTENTIAL TO POSITIVE VALUES, AS A RESULT OF LOWERING THE ENERGY OF THE HIGHEST OCCUPIED MOLECULAR ORBITAL. THE FORMAL POTENTIAL WAS USED AS A MEASUREMENT FOR THE DRIVING FORCE OF CHITOSAN COMPLEXES FOR REDOX REACTIONS.

THE EXOPOLYSACCHARIDE (EPS) SEPARATED FROM THE ENTOMOPATHOGENIC FUNGUS METARHIZIUM ANISOPLIAE WAS DETERMINED BY GEL PERMEATION CHROMATOGRAPHY TO BE HOMOGENEOUS. THE HIGH-PERFORMANCE ANION-EXCHANGE CHROMATOGRAPHY WITH PULSED-AMPEROMETRIC DETECTION (HPAE-PAD) SHOWED A CONTENT OF MONOSACCHARIDES D-GALACTOSAMINE AND D-FUCOSE AT A MOLAR RATIO OF ABOUT 2:1. THE RESULTS OBTAINED FROM FOURIER TRANSFORM-INFRARED SPECTROSCOPY (FT-IR) AND SECOND DERIVATIVE FT-IR SPECTRUM CONFIRMED THE PROPOSED STRUCTURE.