Enhanced production of bioethanol through supercritical carbon dioxide-mediated pretreatment and saccharification of dewaxed bagasse.

The pretreatment and saccharification of dewaxed bagasse (DWB) has been investigated under various reaction conditions ranging 2000 to 3200 psi, at 70 ± 1 °C in supercritical carbon dioxide (SCC). This has been in attempt to transform the DWB into fermentable sugar and bioethanol in high yields. The effect of SCC mediated pretreatment and enzymatic hydrolysis on structural and morphological alterations in DWB has been ascertained through diverse analytical methods. The sugar has been released through cellulase (40 FPU/mL) mediated enzymatic hydrolysis of pretreated DWB in sodium acetate buffer (pH 4.7) within 1 h at SCC 2800 psi, 70 ± 1 °C. The released sugar was subsequently fermented in the presence of yeast (Saccharomyces crevices, 135 CFU) at 28 ± 1 °C over 72 h to afford the bioethanol. The SCC mediated process conducted in acetic acid:water media (1:1) at 2800 psi, 70 ± 1 °C over 6 h has afforded the pretreated DWB with maximum yield towards the production of fermentable sugar and bioethanol. The production of fermentable sugar and bioethanol has been electrochemically estimated through cyclic voltammetry (CV) and square wave voltammetry (SWV) over glassy carbon electrode in KOH (0.1 M). The electrochemical methods were found selective and in close agreement for estimation of the yields (%) of fermentable sugars and bioethanol. The yield (%) of fermentable sugar estimated from CV and SWV were 80.10 ± 5.34 and 79.00 ± 5.09 respectively. Whereas the yield (%) of bioethanol estimated from CV and SWV were 81.30 ± 2.78% and 78.6 ± 1.25% respectively. Present investigation delivers a SCC mediated green and sustainable method of pretreatment of DWB to afford the enhanced saccharification, to produce bioethanol in high yields.

Electrochemical monitoring of congo red degradation using strontium titanate-doped biochar nanohybrids derived photocatalytic plates.

Present investigation demonstrates the development and characterization of strontium titanate (SrTiO3) doped biochar nanohybrid photocatalysts. Biochar nanohybrid was synthesized using an ultrasonic-assisted dispersion technique, which involved dispersing SrTiO3 nanoparticles into activated biochar at a weight ratio of 1:2 (w/w) under ambient conditions. The development of the biochar nanohybrid was verified through a comprehensive analysis of their spectral, microstructural, thermal, electrical, and electrochemical properties. The scanning electron microscopy analysis reveals a surface-associated multiphase morphology of the biochar nanohybrid, attributed to the uniform distribution of SrTiO3 within the activated biochar matrix. Biochar nanohybrid exhibited a reduced optical band gap of 2.77 eV, accompanied by a crystallite size of 32.45. Thermogravimetric analysis revealed the thermal stability of the biochar nanohybrid, as evidenced by a char residue of 70.83% at 1000 °C. The working electrodes derived from biochar nanohybrid have exhibited ohmic behavior and displayed a significantly enhanced DC conductivity (mS/cm) of 1.13, surpassing that of activated biochar (0.53) and SrTiO3 (0.62) at 100 V. The developed biochar nanohybrid were employed for the degradation of congo red dye by exposing the dye solution to photocatalytic plates. These photocatalytic plates were prepared by coating biochar nanohybrid onto glass plates using epoxy-based reactive binders for secure binding. The photodegradation of congo red was evaluated through cyclic voltammetric analysis in a 0.1 M KCl solution at pH 8.0, resulting in an impressive 99.95% photocatalytic efficiency in degrading a congo red solution (50 mg/L). This study presents a novel approach for the fabrication of biochar nanohybrid-derived photocatalytic plates, offering high photocatalytic efficiency for the degradation of congo red dye.

Azide-selective sensor based on tripodal iron complex for direct azide determination in aqueous samples.

A potentiometric azide-selective sensor based on the use of iron(III) hydrotris(3,5-dimethylpyrazolyl)borate acetylacetonate chloride [Tp(Me2)Fe(acac)Cl] as a neutral carrier for an azide-selective electrode is reported. Effect of various plasticizers, viz. o-nitrophenyloctyl ether (o-NPOE), dioctylphthalate (DOP), dibutylphthalate (DBP), and benzylacetate (BA), and an anion excluder, hexadecyltrimethylammonium bromide (HTAB), with [Tp(Me2)Fe(acac)Cl] complex in poly(vinyl chloride) (PVC) were studied. The best performance was obtained with a membrane composition of [Tp(Me2)Fe(acac)Cl]/HTAB/DOP/PVC in a ratio of 5:2:190:100 (w/w). The sensor exhibits significantly enhanced selectivity toward azide ions over the concentration range 6.3 x 10(-7) to 1.0 x 10(-2) M with a lower detection limit of 3.8 x 10(-7) M and a Nernstian slope of 59.4 +/- 1.1 mV decade(-1). Influences of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility, long-term stability and applicability over a wide pH range (3.5-9.0) are demonstrated. The sensor has a response time of 14 s and can be used for at least 45 days without any considerable divergence in the potential response. The proposed electrode shows fairly good discrimination of azide from several inorganic and organic anions. It was successfully applied to the direct determination of azide in orange juice, tea extracts and human urine samples.

A selective membrane electrode for lanthanum(III) ion based on a hexaaza macrocycle derivative as ionophore.

We have developed a highly La(III)-selective PVC membrane electrode based on a hexaaza macrocycle, 8,16-dimethyl-6,14-diphenyl-2,3,4:10,11,12-dipyridine-1,3,5,9,11,13-hexaazacyclohexadeca-3,5,8,11,13,16-hexaene [Bzo2Me2Pyo2(16)-hexaeneN6] (I) as membrane carrier, dibutylbutyl phosphonate (DBBP) as solvent mediator and sodium tetraphenylborate (NaTPB) as lipophilic additive. The best performance was given by the membrane of macrocycle I having a composition 10:260:5:120 (I:DBBP:NaTPB:PVC). The electrode exhibits a Nernstian response to La(III) ion in the concentration range 1.0x10(-1)-7.94x10(-7) M with a slope of 19.8+/-0.2 mV/decade of concentration and a detection limit of 5.62x10(-7) M. The response time of the sensor is 12 s and it can be used over a period of 4 months with good reproducibility. The electrode works well over a pH range of 2.5-10.0 and in partially non-aqueous medium with up to 30% organic content. The sensor was also used as an indicator electrode in potentiometric titration of La(III) ions with EDTA and for determining La(III) concentration in real samples.

Interaction of vanadium(IV) with human serum apo-transferrin.

The interaction of V(IV)O-salts as well as of a few V(IV)O(carrier)n complexes with human serum transferrin (hTF) is studied focusing on the determination of the nature and stoichiometry of the binding of V(IV)O(2+) to hTF, as well as whether the conformation of hTF upon binding to V(IV)O(2+) or to its complexes is changed. Circular dichroism (CD) spectra measured for solutions containing V(IV)O(2+) and apo-hTF, and V(IV)O-maltol and apo-hTF, clearly indicate that hTF-V(IV)O-maltol ternary species form with a V(IV)O:maltol stoichiometry of 1:1. For V(IV)O salts and several V(IV)O(carrier)n complexes (carrier ligand=maltolato, dhp, picolinato and dipicolinato) (Hdhp=1,2-dimethyl-3-hydroxy-4-pyridinone) the maximum number of V(IV)O(2+) bound per mole of hTF is determined to be ~2 or lower in all cases. The binding of V(IV)O to apo-hTF most certainly involves several amino acid residues of the Fe-binding site, and as concluded by urea gel electrophoresis experiments, the formation of (V(IV)O)2hTF species may occur with the closing of the hTF conformation as is the case in (Fe(III))2hTF, which is an essential feature for the transferrin receptor recognition.

Evaluation of the binding of oxovanadium(IV) to human serum albumin.

The understanding of the biotransformations of insulin mimetic vanadium complexes in human blood and its transport to target cells is an essential issue in the development of more effective drugs. We present the study of the interaction of oxovanadium(iv) with human serum albumin (HSA) by electron paramagnetic resonance (EPR), circular dichroism (CD) and visible absorption spectroscopy. Metal competition studies were done using Cu(II) and Zn(II) as metal probes. The results show that V(IV)O occupies two types of binding sites in albumin, which compete not only with each other, but also with hydrolysis of the metal ion. In one of the sites the resulting V(IV)O-HSA complex has a weak visible CD signal and its X-band EPR spectrum may be easily measured. This was assigned to amino acid side chains of the ATCUN site. The other binding site shows stronger signals in the CD in the visible range, but has a hardly measurable EPR signal; it is assigned to the multi metal binding site (MBS) of HSA. Studies with fatted and defatted albumin show the complexity of the system since conformational changes, induced by the binding of fatty acids, decrease the ability of V(IV)O to bind albumin. The possibility and importance of ternary complex formation between V(IV)O, HSA and several drug candidates - maltol (mal), picolinic acid (pic), 2-hydroxypyridine-N-oxide (hpno) and 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone (dhp) was also evaluated. In the presence of maltol the CD and EPR spectra significantly change, indicating the formation of ternary VO-HSA-maltol complexes. Modeling studies with amino acids and peptides were used to propose binding modes. Based on quantitative RT EPR measurements and CD data, it was concluded that in the systems with mal, pic, hpno, and dhp (V(IV)OL(2))(n)(HSA) species form, where the maximum value for n is at least 6 (mal, pic). The degree of formation of the ternary species, corresponding to the reaction V(IV)OL(2) + HSA -->/<-- V(IV)OL(2)(HSA) is hpno > pic ≥ mal > dhp. (V(IV)OL)(n)(HSA) type complexes are detected exclusively with pic. Based on the spectroscopic studies we propose that in the (V(IV)OL(2))(n)(HSA) species the protein bounds to vanadium through the histidine side chains.

Development of electrochemical sensors for nano scale Tb(III) ion determination based on pendant macrocyclic ligands.

The two macrocyclic pendant ligands 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetramethylacrylate-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-di ene (L(1)) and 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetra(2-cyano ethane)-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-diene (L(2)) have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Tb(III) ions. Effects of various plasticizers and anion excluders were studied in detail and improved performance was observed. The best performance was obtained for the membrane sensor having a composition of L(1): PVC:1-CN:NaTPB in the ratio of 6: 32: 58: 4 (w/w; mg). The performance of the membrane based on L(1) was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Tb(3+) ions with limits of detection of 3.4 x 10(-8)mol L(-1) for PME and 5.7 x 10(-9)mol L(-1) for CGE. The response time for PME and CGE was found to be 10s and 8s, respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.0-7.5 for PME and 2.0-8.5 for CGE. The CGE has found to work satisfactorily in partially non-aqueous media upto 30% (v/v) content of methanol, ethanol and 20% (v/v) content of acetonitrile and could be used for a period of 5 months. The CGE was used as indicator electrode in the potentiometric titration of Tb(3+) ions with EDTA and in determination of fluoride ions in various samples. It can also be used in direct determination of Tb(3+) ions in tap water and various binary mixtures with quantitative results.

Polymeric membrane sensors based on Cd(II) Schiff base complexes for selective iodide determination in environmental and medicinal samples.

The two cadmium chelates of schiff bases, N,N'-bis(salicylidene)-1,4-diaminobutane, (Cd-S(1)) and N,N'-bis(salicylidene)-3,4-diaminotoluene (Cd-S(2)), have been synthesized and explored as ionophores for preparing PVC-based membrane sensors selective to iodide(I) ion. Potentiometric investigations indicate high affinity of these receptors for iodide ion. Polyvinyl chloride (PVC)-based membranes of Cd-S(1) and Cd-S(2) using as hexadecyltrimethylammonium bromide (HTAB) cation discriminator and o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), acetophenone (AP) and tributylphosphate (TBP) as plasticizing solvent mediators were prepared and investigated as iodide-selective sensors. The best performance was shown by the membrane of composition (w/w) of (Cd-S(1)) (7%):PVC (31%):DBP (60%):HTAB (2%). The sensor works well over a wide concentration range 5.3x10(-7) to 1.0x10(-2)M with Nernstian compliance (59.2mVdecade(-1) of activity) within pH range 2.5-9.0 with a response time of 11s and showed good selectivity for iodide ion over a number of anions. The sensor exhibits adequate life (3 months) with good reproducibility (S.D.+/-0.24mV) and could be used successfully for the determination of iodide content in environmental water samples and mouth wash samples.

Tripodal chelating ligand-based sensor for selective determination of Zn(II) in biological and environmental samples.

Potassium hydrotris(N-tert-butyl-2-thioimidazolyl)borate [KTtt-Bu] and potassium hydrotris(3-tert-butyl-5-isopropyl-l-pyrazolyl)borate [KTpt-Bu,i-Pr] have been synthesized and evaluated as ionophores for preparation of a poly(vinyl chloride) (PVC) membrane sensor for Zn(II) ions. The effect of different plasticizers, viz. benzyl acetate (BA), dioctyl phthalate (DOP), dibutyl phthalate (DBP), tributyl phosphate (TBP), and o-nitrophenyl octyl ether (o-NPOE), and the anion excluders sodium tetraphenylborate (NaTPB), potassium tetrakis(p-chlorophenyl)borate (KTpClPB), and oleic acid (OA) were studied to improve the performance of the membrane sensor. The best performance was obtained from a sensor with a of [KTtt-Bu] membrane of composition (mg): [KTtt-Bu] (15), PVC (150), DBP (275), and NaTPB (4). This sensor had a Nernstian response (slope, 29.4+/-0.2 mV decade of activity) for Zn2+ ions over a wide concentration range (1.4x10(-7) to 1.0x10(-1) mol L(-1)) with a limit of detection of 9.5x10(-8) mol L(-1). It had a relatively fast response time (12 s) and could be used for 3 months without substantial change of the potential. The membrane sensor had very good selectivity for Zn2+ ions over a wide variety of other cations and could be used in a working pH range of 3.5-7.8. The sensor was also found to work satisfactorily in partially non-aqueous media and could be successfully used for estimation of zinc at trace levels in biological and environmental samples.

Ytterbium-selective polymeric membrane electrode based on substituted urea and thiourea as a suitable carrier.

Plasticized membranes using 1-phenyl-3-(2-thiazolyl)-2-thiourea (PTT) and 1-phenyl-3-(2-thiazolyl)-2-urea (PTU) have been prepared and explored as ytterbium ion-selective sensors. Effect of various plasticizers, viz. chloronaphthalene (CN), o-nitrophenyloctyl ether (o-NPOE), dibutylphthalate (DBP), dioctylsebacate (DOS) and anion excluders, sodium tetraphenylborate (NaTPB) and oleic acid (OA) was studied and improved membrane performance was observed. Optimum performance was noted with membrane of PTT having composition of PTT (3.5):PVC (80):DOS (160):NaTPB (1.5) in mg. The sensor works satisfactorily in the concentration range 1.2x10(-7) to 1.0x10(-2) M (detection limit 5.5x10(-8) M) with a Nernstian slope of 19.7 mV decade(-1) of activity. Wide pH range (3.0-8.0), fast response time (10 s), non-aqueous tolerance (up to 20%) and adequate shelf life (12 weeks) indicate the vital utility of the proposed sensor. The proposed electrode comparatively shows good selectivity for Yb3+ ion with respect to alkali, alkaline earth, transition and rare earth metals ions and can be used for its determination in binary mixtures and sulfite determination in white and red wine samples.

A bromide selective polymeric membrane electrode based on Zn(II) macrocyclic complex.

A novel bromide ion-selective PVC membrane sensor based on 2,3,10,11-tetraphenyl-1,4,9,12-tetraazacyclohexadeca-1,3,9,11-tetraene zinc(II)complex (I) as carrier has been developed. The electrode exhibited wide working concentration range 2.2 x 10(-6) to 1.0 x 10(-1)M and a limit of detection as 1.4 x 10(-6)M with a Nernstian slope of 59.2+/-0.5 mV per decade. The response time of electrode was 20s over entire concentration range. The electrode possesses the advantages of low resistance, fast response and good selectivities for bromide over a variety of other anions and could be used in a pH range of 3.5-9.5. It was successfully used as an indicator electrode in the potentiometric titration of bromide ions with silver ion and also in the determination of bromide in real samples.

Cobalt(II)-selective membrane sensor based on a [Me2(13)dieneN4] macrocyclic cobalt complex.

A new poly(vinyl chloride)-based membrane was fabricated with the cobalt(II) complex of 2,4-dimethyl-1,5,8,11-tetraazacyclotrideca-1,4-diene [Me2(13)dieneN4] as an ion carrier. The membrane composition was Co2+ complex/PVC/NaTPB/DBP 15:50:15:20 (w/w). The sensor exhibited a Nernstian response for Co2+ ions over a wide concentration range (7.94x10(-6)-1.0x10(-1) M) at pH 2.5-7.0, a response time of 10 s, and it could be used for 3 months without any significant divergence in potential. The proposed membrane sensor exhibited good selectivity for Co2+ over a wide variety of other metal ions and in mixtures containing up to 25% (v/v) non-aqueous content. The sensor was successfully used as an indicator electrode in the potentiometric titration of Co2+ with EDTA and the direct determination of Co2+ in real samples.

Strontium(II)-selective electrode based on a macrocyclic tetraamide.

A new PVC membrane electrode based on 5,7,12,14-dibenzo-2,3,9,10-tetraoxa-1,4,8,11-tetraazacyclotetradecane (I) as an ion carrier, o-nitrophenyloctyl ether (o-NPOE) as solvent mediator and sodium tetraphenylborate (NaTPB) as lipophilic additive was fabricated and investigated as Sr(2+)-selective electrode. The best performance was exhibited by the membrane having composition 8:200:4:120 (I:o-NPOE:NaTPB:PVC). The electrode exhibited a Nernstian response for strontium ion over a wide concentration range 3.98 x 10(-6) to 1.0 x 10(-1)M with a slope of 29.0+/-0.1 mV/decade of concentration and a detection limit of 2.82 x 10(-6)M. It showed a response time of less than 10s and could be used for at least 3 months without any divergence in potential. The proposed electrode showed a good discriminating ability towards strontium(II) ion over a wide variety of other metal ions including alkali, alkaline earth, transition, and heavy metal ions. The electrode can be used in the pH range of 2.5-10.5 and in mixtures containing up to 35% (v/v) non-aqueous content. It was used as an indicator electrode in potentiometric titration of strontium ion against EDTA.

Selective electrochemical sensor for copper (II) ion based on chelating ionophores.

Plasticized membranes using 3-(2-pyridinyl)-2H-pyrido[1,2,-a]-1,3,5-triazine-2,4(3H)-dithione (L1) and acetoacetanilide (L2) have been prepared and explored as Cu2+-selective sensors. Effect of various plasticizers, viz. chloronaphthalene (CN), benzyl acetate (BA), o-nitrophenyloctyl ether (o-NPOE), and anion excluders, sodium tetraphenylborate (NaTPB) and oleic acid (OA) was studied in detail and improved performance was observed at several instances. Optimum performance was observed with dithione derivative (L1) having a membrane composition of L1 (5):PVC (120):o-NPOE (240):OA (10). The sensor works satisfactorily in the concentration range 5.0 x 10(-8) to 1.0 x 10(-2) M (detection limit 4.0 x 10(-8) M) with a Nernstian slope of 29.5 mV decade(-1) of activity. Wide pH range (3.0-9.5), fast response time (12s), non-aqueous tolerance (up to 20%) and adequate shelf life (4 months) indicate the vital utility of the proposed sensor. The potentiometric selectivity coefficient values as determined by match potential method (MPM) indicate good response for Cu2+ in presence of interfering ions. The proposed electrode comparatively shows good selectivity with respect to alkali, alkaline earth, transition and some rare earth metals ions. The electrode was used for the determination of copper in different milk powder, water samples and as indicator electrode in potentiometric titration of copper ion with EDTA.