Preparation, Characterization and Study of the Dissociation of Naproxen from Its Chitosan Salt.

Salts of naproxen (NAP) with chitosan (CTS) and reticulated chitosan (CEP) were prepared under optimized conditions to maximize the yield of reaction. The objective was to evaluate the dissociation in water, which can guide studies of release of the drug from biopolymeric salts in pharmaceutical applications. Higher salification was found after 24 h of reaction at 60 °C in a molar ratio 1:1.05 (CTS:NAP, mol/mol), resulting in a degree of substitution (DS) of 17% according to 13C NMR, after neutralization of the -NH2 group of the biopolymer by the carboxylic group of the drug. The presence of NAP salt is evidenced by FTIR bands related to the -NH3+ group at 856 cm-1, a decrease in crystallinity index in XRD diffractograms as well as changes in mass loss ratios (TG/DTG/DTA) and increased thermal stability of the salt regarding CTS itself. The CEPN crosslinked salt presented a DS = 3.6%, probably due to the shielding of the -NH2 groups. Dissociation studies revealed that at pH 2.00, dissociation occurred faster when compared to at pH 7.00 in the non-reticulated salt, while the opposite was observed for the reticulated one.

Screen-printed disposable electrodes using graphite-polyurethane composites modified with magnetite and chitosan-coated magnetite nanoparticles for voltammetric epinephrine sensing: a comparative study.

Disposable screen-printed electrodes based on the use of graphite-polyurethane composites modified with magnetite nanoparticles (MNP-SPE) or chitosan-coated magnetite nanoparticles (CHMNP-SPE) are described. The MNP and CHMNP were synthetized and comparatively characterized by TEM, XRD, FTIR, and TGA/DTG. The MNP-SPE and CHMNP-SPE were characterized by SEM and EDX. After optimization of the MNP percentage in MNP-SPE, the materials were electrochemically characterized by cyclic voltammetry, EIS, and chronocoulometry. The electrodes were tested for their performance towards sensing of epinephrine (EP). The CHMNP-SPE is found to have better electrochemical responses in comparison to the MNP-SPE. This is assumed to be due to the chitosan coating which also protects the MNPs from oxidation under air and at different applied potential fields. The performances of the MNP-SPE and CHMNP-SPE were studied by DPV after optimization of equilibration time and DPV parameters. Response is linear in the 0.1-0.8 µM EP concentration range, at 0.03 V (vs. pseudo-Ag/AgCl), and the detection limit is 25 nM for the MNP-SPE. The linear response for the CHMNP-SPE was 0.1-0.6 µM, at 0.0 V (vs. pseudo-Ag/AgCl), and a LOD of 14 nM was achieved. The devices were used for the quantification of EP in synthetic urine and in cerebrospinal synthetic fluids. Recoveries from spiked samples are in the 95.6-102.2% range for the CHMNP-SPE and in the 98.3-109% range for MNP-SPE. The stability of the respective sensors was investigated and compared over a period of 5 months. The EP peak currents were found to decrease by only 4% for the CHMNP-SPE, while the MNP-SPE lost 23% of its EP peak current. Accordingly, the CHMNP-SPE was chosen as the most stable and sensitive sensor for EP. Graphical abstract Schematic figure of modification of a graphite-polyurethane screen-printed composite electrode with magnetite nanoparticles (MNPs) and chitosan-coated magnetite nanoparticles (CHMNPs) for the voltammetric determination of epinephrine (EP). Improved response of CHMNP-SPE (black voltammogram) in comparison to MNP-SPE (red voltammogram) was attributed to the protection of MNP from oxidation.

Nanodiamond based surface modified screen-printed electrodes for the simultaneous voltammetric determination of dopamine and uric acid.

The electroanalytical detection of the neurotransmitter dopamine (DA) in the presence of uric acid (UA) is explored for the first time using commercially procured nanodiamonds (NDs). These are electrically wired via surface modification upon screen-printed graphite macroelectrodes (SPEs). The surface coverage of the NDs on the SPEs was explored in order to optimize electroanalytical outputs to result in well-resolved signals and in low limits of detection. The (electro)analytical outputs are observed to be more sensitive than those achieved at bare (unmodified) SPEs. Such responses, previously reported in the academic literature have been reported to be electrocatalytic and have been previously attributed to the presence of surface sp2 carbon and oxygenated species on the surface of the NDs. However, XPS analysis reveals the commercial NDs to be solely composed of nonconductive sp3 carbon. The low/negligible electroconductivity of the NDs was further confirmed when ND paste electrodes were fabricated and found to exhibit no electrochemical activity. The electroanalytical enhancement, when using NDs electronically wired upon SPEs, is attributed not to the NDs themselves being electrocatalytic, as reported previously, but rather changes in mass transport where the inert NDs block the underlying electroactive SPEs and create a random array of graphite microelectrodes. The electrode was applied to simultaneous sensing of DA and UA at pH 5.5. Figures of merit include (a) low working potentials of around 0.27 and 0.35 V (vs. Ag/AgCl); and (b) detection limits of 5.7 × 10-7 and 8.9 × 10-7 M for DA and UA, respectively. Graphical abstract The electroanalytical enhancement of screen-printed electrodes modified with inert/non-conductive nanodiamonds is due to a change in mass transfer where the inert nanodiamonds facilitate the production of a random microelectrode array.

Pen sensor made with silver nanoparticles decorating graphite-polyurethane electrodes to detect bisphenol-A in tap and river water samples.

Rapid, on-site detection of emerging pollutants is critical for monitoring health threats and the environment, especially if performed through autonomous systems. In this paper, we report on a new design of a complete electrochemical system whose working (WE), auxiliary (AE) and reference (RE) electrodes were obtained on a pen (PEN Sensor) made with graphite:polyurethane (GPUE). Working electrodes were decorated with spherical, ca. 200 nm silver nanoparticles (AgNPs) reduced on graphite using the polyol method. Differential pulse voltammetry (DPV) was used to detect bisphenol-A (BPA) in a linear range from 2.5 to 15 µmol L-1 with detection limit of 0.24 µmol L-1. The PEN Sensor could also detect bisphenol-A in tap and river water samples, with satisfactory reproducibility and repeatability, while common interferents did not affect electrooxidation of bisphenol-A. The high sensitivity and rapid detection are suitable for real-time analysis and in loco monitoring of emerging pollutants. With their robustness and versatility, PEN Sensors such as those fabricated here may be integrated into futuristic smart robotic systems.

Developing a screen-printed graphite-polyurethane composite electrode modified with gold nanoparticles for the voltammetric determination of dopamine.

A screen-printed electrode (SPGPUE) was prepared with graphite-polyurethane composite ink containing gold nanoparticles (AuNPs), resulting in a screen-printed graphite-polyurethane composite electrode modified with gold nanoparticles (SPGPUE-AuNPs). Gold nanoparticles were prepared by the citrate method and extracted from the water medium since polyurethane is not compatible with humidity. After extraction to chloroform, they were characterized via transmission electron microscopy (TEM). The presence of gold on the SPGPUE-AuNP surface was confirmed via SEM and EDX analyses, while thermogravimetry revealed the presence of approximately 3.0% (m/m) gold in the composite. An electrochemical pretreatment in 0.10 mol L-1 phosphate buffer (pH 7.0) with successive cycling between -1.0 V and 1.0 V (vs. pseudo-Ag/AgCl) under a scan rate of 200 mV s-1 and 150 cycles was required in order to provide a suitable electrochemical response for the voltammetric determination of dopamine. After the optimization of the parameters of differential pulse voltammetry (DPV), an analytical curve was obtained within a linear dynamic range of 0.40-60.0 µmol L-1 and detection limit (LOD) of 1.55 ×10-8 mol L-1 for dopamine at the SPGPUE-AuNP. A non-modified SPGPUE was used for comparison and a linear range was obtained between 2.0 and 10 µmol L-1 with an LOD of 2.94 × 10-7 mol L-1. During the dopamine determination in cerebrospinal synthetic fluid (CSF), recoveries between 89.3 and 103% were achieved. There were no significant interferences from ascorbic acid and uric acid, but some from epinephrine due to the structural similarity.

A new look towards the thermal decomposition of chitins and chitosans with different degrees of deacetylation by coupled TG-FTIR.

Chitins and Chitosans with different degrees of deacetylation (DD¯) were analyzed for the first time by thermogravimetry coupled to infrared spectroscopy TG-FTIR in order to evaluate the effect of DD¯ on the thermal decomposition process. DD¯ values of chitins and chitosans were determined by 1H-NMR and structural difference were investigated by FTIR, SEM and XRD. Thermal stability of chitosan with 98, 87, 71% DD¯, chitins with 47 and 27% DD¯ and commercial α-chitin were evaluated. Thermal decomposition of chitosans occurs in two steps, while for chitins occurs predominantly in first stage under air atmosphere. Commercial chitin thermally decomposed at lower temperatures than highly deacetylated chitosan. A faster thermal degradation process was found for chitins, except for commercial sample. TG-FTIR of evolved gas evidenced a complex gaseous mixture mainly composed by ammonia, acetic acid, acetamide, water, monoxide and carbon dioxide in proportions that are deeply dependent on the DD¯.

Characterization, solubility and biological activity of amphihilic biopolymeric Schiff bases synthesized using chitosans.

Chitosans are versatile biopolymers recognized for their wide range of biological activities. However, the low solubility in neutral and basic solutions restricts the applications. Thus amphiphilic biopolymeric Schiff bases from chitosans, salicylaldehyde and glycidol were successfully synthesized and characterized using 1H-NMR, UV/Vis, FTIR, TG/DTG-DTA and tested for their antimicrobial activities against plant pathogenic microorganisms and human breast cancer cells (MCF-7). Overall, functionalization of chitosans with salicylaldehyde and glycidol with different molecular weight (Mw¯) was performed to improve the biological actives of chitosans. Thus the biological activity of the new amphiphilic compounds prepared in this work were evaluated regarding microorganisms with agricultural relevance and tumor cells. The biopolymeric amphiphilic Schiff bases showed significant effects against Pseudomonas syringae (IC50 < 5 µg mL-1) compared to the natural chitosans with medium Mw¯ (CHM 223 kDa) and low Mw¯ (CHL 64 kDa), which had IC50 values of 42 and 37 µg mL-1, respectively. In addition, they improved antitumor activity against tumor cells compared to the natural chitosan.

Chemical modification of alginate with cysteine and its application for the removal of Pb(II) from aqueous solutions.

It has been synthesized, characterized and tested a new biomaterial AlgS (sodium alginate functionalized with cysteine) to remove Pb(II) in aqueous media. The maximum Pb(II)-sorption capacity of AlgS (Qmax = 770 mg·g-1) is between almost two and nine times higher than other alginate-materials reported in the literature. Techniques, such as TGA/DSC, SEM/EDS, BET, FTIR, UV-Vis, XRD and 13C solid state-NMR have been used to study the chemical-modification of alginate at oxidation and aminofication stages. The formation of the imine intermediate (C=N), after 24 h of reaction was identified by a UV band at 348 nm. Typical IR-bands of AlgS were identified at 2970, 955, 949 and 1253 cm-1 which are associated to CH, SPb, SH and CN stretching vibrations, respectively. 13C solid state-NMR spectra of AlgS, show peaks at 33-38 ppm and 55-60 ppm associate to δ (HS-CH2-) of cysteine and δ (CN) respectively. The ΔH° and ΔG° negative values for Pb(II) sorption indicate that it is an exothermic process and occur spontaneously. Finally, it was found that the Pb(II) sorption on AlgS is significantly affected by the presence of cationic (Na+, Mg2+ and Al3+) and anionic (Cl-, NO3-) co-ions.

Chemical modification of sodium alginate with thiosemicarbazide for the removal of Pb(II) and Cd(II) from aqueous solutions.

A new material (AlgOx-TSC), based on alginate (Alg) chemically modified with thiosemicarbazide (TSC), has been synthesized and tested as an effective biomaterial to remove Pb(II) and Cd(II) ions in aqueous solutions. The synthesis was carried out by controlling the following steps, i/partial oxidation process of alginate in NaIO4 to obtain AlgOx, ii/reacting of AlgOx, at 40-45 °C, with TSC in NaBH4. AlgOx-TSC has been characterized by Field Emission Scanning Electron Microscopy (FESEM/EDS), Fourier Transform Infrared Spectroscopy (ATR-IR), solid state 13C NMR spectroscopy and Point of Zero Charge (pHPZC) measuremenmts. In order to enhance the sorption process, the effect of contact time, sorbent dosage, initial concentration and reusability of the novel sorbent were investigated becoming the AlgOx-TSC a promising material capable of removing high concentrations of heavy metal ions such as Pb(II) (up to 950 mg/g at pH 3) and Cd(II) (up to 300 mg/g at pH 7) in aqueous solutions.

Differential pulse anodic voltammetric determination of lithium ions in pharmaceutical formulations using a carbon paste electrode modified with spinel-type manganese oxide.

The use of the differential pulse voltammetry for the determination of lithium ions in pharmaceutical samples using a carbon paste electrode modified with spinel-type manganese oxide has been examined. The best voltammetric response was reached for a modified electrode in borate buffer solution of pH 9.0 and submitted to a scan rate of 5 mV s(-1) and a pulse amplitude of 50 mV. This electroanalytical procedure was able to determine lithium ions in the concentration range of 8.0 x 10(-5)-1.0 x 10(-2) mol l(-1) even in the presence of several alkali metals (1.0 x 10(-3) mol l(-1)) with a detection limit of 7.1 x 10(-7) mol l(-1). Rapidity, precise and good selectivity were also found for the determination of lithium ions in pharmaceutical formulations.

Flow injection amperometric determination of dipyrone in pharmaceutical formulations using a carbon paste electrode.

The behavior of a carbon paste electrode was investigated as an amperometric detector for the determination of dipyrone by flow injection analysis (FIA). The electrode presented low cost and easy construction by simple mixing of graphite powder and mineral oil. Initially, an electrochemical study of the dipyrone oxidation at a carbon paste electrode has been developed before its use in the FIA system. The oxidation currents monitored at +0.35 V versus Ag/AgCl, were proportional to the dipyrone concentrations. Experimental parameters, such as nature of supporting electrolyte, pH of the carrier solution, flow rate, sample volume injection and probable interferents were investigated. Under the best experimental conditions selected, the calibration curve for dipyrone was linear in the concentration range from 4.91 x 10(-6) to 2.50 x 10(-4) M l(-1) (I(anodic)/microA)=0.056+81.06 [dipyrone]) with a detection limit of 2.07 x 10(-6) M l(-1). Recoveries ranged from 93.8 to 100.8% and an analytical frequency of 130 h(-1) was achieved. The proposed flow procedure has been satisfactorily applied to the determination of dipyrone in several pharmaceutical formulations.

Carbon paste electrode modified with copper (II) phosphate immobilized in a polyester resin for voltammetric determination of L-ascorbic acid in pharmaceutical formulations.

A carbon paste electrode modified with copper(II) phosphate immobilized in a polyester resin (CuP-Poly) is proposed for voltammetric determination of L-ascorbic acid in pharmaceutical formulations. The modified electrode allows the detection of L-ascorbic acid at lower anodic potentials than observed at unmodified electrodes. Several parameters that can influence the voltammetric response of the proposed electrode such as carbon paste composition, pH, scan rate, and possible interference were investigated. The peak current was proportional to the concentration of ascorbic acid in the range 2.0 x 10(-5) to 3.2 x 10(-3) mol L(-1) with a detection limit of 1.0 x 10(-5) mol L(-1). The stability and repeatability of the electrode for the determination of L-ascorbic acid are also discussed. Amperometric response was also recorded for electrocatalytic oxidation of the L-ascorbic acid. Concentrations of the vitamin C in pharmaceutical formulations (tablets) measured using the modified electrode and a titrimetric method are in agreement at the 95% confidence level and within an acceptable range of error.

Evaluation of a carbon paste electrode modified with organofunctionalized amorphous silica in the cadmium determination in a differential pulse anodic stripping voltammetric procedure.

The determination of cadmium using a carbon paste electrode modified with organofunctionalized amorphous silica with 2-benzothiazolethiol was investigated. The Cd(II) oxidation peak was observed around -0.80 V (vs. SCE) in phosphate buffer (pH 4.0) in differential pulse anodic stripping voltammetry. The best results were obtained under the following optimized conditions: 1 min accumulation time, 50 mV pulse amplitude, 20 mV s(-1) scan rate in phosphate buffer pH 4.0. Using such parameters a linear dynamic range from 5.6 x 10(-7) to 3.5 x 10(-5) mol l(-1) Cd(II) was observed with a sensitivity of 2.83 microA mol(-1) l, limit of detection 1.0 x 10(-7) mol l(-1). Cd(II) spiked in a natural water sample was determined with 99% mean recovery at 10(-7) mol l(-1) level. Interference were also evaluated.