Citrullus colocynthis fruit extract as effective eco-friendly corrosion inhibitor in a hydrochloric acid pickling medium for carbon steel by using both experimental and theoretical studies.

The present study focuses on an environmental approach based on the use of an eco-friendly corrosion inhibitor from the Citrullus colocynthis fruit extract for enhancement corrosion resistance of carbon steel (C-S) in acid medium as an alternative to various organic and non-organic chemical inhibitors. The evaluation of the inhibition properties of the fruit methanolic extract of Citrullus colocynthis (CCE) were performed in molar hydrochloric acid (1 M HCl) medium using gravimetric and electrochemical (potentiodynamic polarization and AC impedance) techniques as well as surface analyses. CCE is rich in amino acids, mainly citrulline and ß-(pyrazo-1-yl)-L-analine molecules. Based on the weight loss evaluation, the results demonstrated that this plant extract acts as an effective corrosion inhibitor and a protection level of 93.6% was attained at 500 ppm of CCE after 6 h of metal exposure at 303 K. According to polarization curves, CCE functions as a mixed-type inhibitor. In addition, AC impedance analyses have shown that the incorporation of CCE into the corrosive solution leads to a decrease in load capacity, while improving the charge/discharge function at the interface. This suggests the possibility of the formation of an adsorbed layer on the C-S surface. In addition, scanning electron microscope (SEM) observation, contact angle measurements, and Fourier-transform infrared spectroscopy (FTIR) analyses supported the development of a protective film over CS substrate surface afterwards addition of CCE. Langmuir and/or Temkin isotherms can be used to characterize the adsorption of this organic inhibitor on the C-S surface. X-ray photoelectron spectroscopy (XPS) has revealed that the inhibiting effect of CCE on the corrosion of C-S in 1 M HCl solution is mainly controlled by a chemisorption process and the inhibitive layer is composed of an iron oxide/hydroxide mixture where CCE molecules are incorporated. In order to understand the relationship between the molecular structure and anti-corrosion effectiveness of these inhibitor molecules, quantum chemical studies were carried out using density functional theory (DFT) and molecular dynamics (MD) simulation.

Eco-friendly anti-corrosion performance of chitosan modified with fused heterocyclic compound on mild steel in acidic medium.

This study aims to explore the prevention of chitosan modified with a fused heterocyclic compound as a sustainable corrosion inhibitor for mild steel in 1 M HCl. Electrochemical instruments, including potentiodynamic polarization techniques, and electrochemical impedance spectroscopy (EIS), were employed to evaluate the corrosion protection performance. The outcomes showed that the chitosan modified with a fused heterocyclic compound has outstanding inhibition performance, with an inhibition effectiveness of 98.25 % at 100 ppm. The anti-corrosion features of modified chitosan were ascribed to the presence of hetero atoms in modified chitosan composite which leads to the creation of a protective layer, The modified chitosan composite behaved as mixed-typed inhibitors, as shown by the PDP results. The modified chitosan composite adsorbs on mild steel in the investigated corrosive media via chemisorption interactions, and its adsorption followed the Langmuir adsorption model. Furthermore, increasing the temperature from 303 to 333 K enhanced the corrosion rate, most likely due to the desorption of the inhibitor agent from the steel surface.

Frontiers and advances in N-heterocycle compounds as corrosion inhibitors in acid medium: Recent advances.

The acid solution is widely used in chemical cleaning, oil well acidifying, and other fields, which also brings the problem of metal corrosion that cannot be underestimated. However, adding an inhibitor is one of the most convenient and effective ways to slow down metal corrosion. N-heterocyclic compounds with high stability and durability, in line with the strategy of sustainable development, have been widely studied in an acidic environment. Imidazole, pyridine, and quinoline compounds, as the most commonly used corrosion inhibitors, can form a compact protective film via π electron cloud shifting towards the N atoms to generate coordination function. In particular, flexible modifiability makes N-heterocyclic compounds adapt to different corrosion environments readily, conducive to the formation of chemical bonds between compounds with metal surfaces to be better adsorption, so as to avoid the blemish of traditional inhibitors (such as inorganic salt and organic amines inhibitors) due to excessive usage, surface roughness of metal or environmental factor (for instance, temperature, pH and metallic) causing loose bonding between film and metal surface. More importantly, the efficient corrosion inhibition and toxicity of N-heterocyclic compounds have close to do with their own functional groups. Combined with the latest research achievement, the effects of different substituents on the corrosion inhibition and corrosion inhibition mechanisms were systematically reviewed in the acid-corrosive solution of imidazole, pyridine, and quinoline and their derivatives in this review article, respectively. In addition, the application and function of density functional theory in predicting the corrosion inhibition effect of corrosion inhibitors are also discussed. The future development trend was prospected according to the summarized research results.

Graphene Oxide versus Carbon Nanofibers in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Films: Degradation in Simulated Intestinal Environments.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a microbial biodegradable polymer with a broad range of promising industrial applications. The effect of incorporation of low amounts (1% w/w) of carbon nanomaterials (CBNs) such as 1D carbon nanofibers (CNFs) or 2D graphene oxide (GO) nanosheets into the PHBV polymer matrix affects its degradation properties, as it is reported here for the first time. The study was performed in simulated gut conditions using two different media: an acidic aqueous medium (pH 6) and Gifu anaerobic medium. The results of this study showed that the incorporation of low amounts of filamentous 1D hydrophobic CNFs significantly increased the degradability of the hydrophobic PHBV after 3 months in simulated intestinal conditions as confirmed by weight loss (~20.5% w/w in acidic medium) and electron microscopy. We can attribute these results to the fact that the long hydrophobic carbon nanochannels created in the PHBV matrix with the incorporation of the CNFs allowed the degradation medium to penetrate at ultrafast diffusion speed increasing the area exposed to degradation. However, the hydrogen bonds formed between the 2D hydrophilic GO nanosheets and the hydrophobic PHBV polymer chains produced a homogeneous composite structure that exhibits lower degradation (weight loss of ~4.5% w/w after three months in acidic aqueous medium). Moreover, the water molecules present in both degradation media can be linked to the hydroxyl (-OH) and carboxyl (-COOH) groups present on the basal planes and at the edges of the GO nanosheets, reducing their degradation potential.

Interactions study of 1,2,4-triazole derivatives in acid medium using molecular dynamics.

We investigated the interaction of some 1,2,4-triazoles derivatives: 4-amino-3-methylthio-5-phenyl-4H-1,2,4-triazole 1, 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol 2 A, 4-amino-5-phenyl-2H-1,2,4-triazole-3-thione 2B, and 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol 2 C (respectively MTE 1, TL 2 A, TN 2B and TL 2 C) using the molecular dynamics simulation. First, we employed this method to predict the total energies in vacuum and in solutions (water and acid media). Then, we calculated the MD parameters: interaction energies and angle parameters. We have also evaluated the conformations of these molecules in gas and in solutions. Next, we compared the calculated results in water with those in acid solution. Our simulated results prove that the presence of intermolecular hydrogen bond increases the interaction energies in the tautomer thione 2B. We confirm that the TN 2B reaches its high stable conformation state in the solution environment. The calculations confirm that the compound MTE 1 has a spatial conformation state and shows high interaction energy in acid medium. Our molecular dynamics results complete very well our quantum chemical calculations. Communicated by Ramaswamy H. Sarma.

Investigation of mitochondrial protein expression profiles of Yarrowia lipolytica in response to citric acid production.

Nitrogen-limiting condition is essential for citric acid production by Yarrowia lipolytica. Mitochondrial protein expression profiles of Y. lipolytica IMUFRJ 50,682 cells cultivated in biomass proliferation medium (YPG medium, yeast extract, peptone and glycerol) and citric acid production medium (CA medium) were analyzed to identify differences in expressed proteins in response to medium composition. The identification of 45 proteins in mitochondria of YPG medium cells and 48 proteins in mitochondria of CA medium cells were possible with proteomic analyses. Only 11 proteins were common to both conditions, showing a different expression pattern in relation to limiting and non-limiting nitrogen conditions. For both conditions, most proteins (52%-CA medium, 46%-YPG medium) were related to energy metabolism. CA medium cells expressed more carbohydrate metabolism proteins (six proteins) then YPG medium cells (three proteins) and the opposite was detected for translation proteins.

Customised structural, optical and antibacterial characteristics of cinnamon nanoclusters produced inside organic solvent using 532 nm Q-switched Nd:YAG-pulse laser ablation.

Biomedical values of organic natural cinnamon that are buried in their bulk counterpart can be exposed and customised via nanosizing. Based on this factor, a new type of spherical cinnamon nanoclusters (Cin-NCs) were synthesised using eco-friendly nanosecond pulse laser ablation in liquid (PLAL) approach. As-grown nontoxic Cin-NCs suspended in the citric acid of pH 4.5 (acted as organic solvent) were characterised thoroughly to evaluate their structural, optical and bactericidal properties. The effects of various laser fluences (LF) at the fixed wavelength (532 nm) on the physiochemical properties of these Cin-NCs were determined. The FTIR spectra of the Cin-NCs displayed the symmetric-asymmetric stretching of the functional groups attached to the heterocyclic/cinnamaldehyde compounds. The HR-TEM image of the optimum sample revealed the nucleation of the crystalline spherical Cin-NCs with a mean diameter of approximately 10 ± 0.3 nm and lattice fringe spacing around 0.14 nm. In addition, the inhibition zone diameter (IZD) and optical density (OD600) of the proposed Cin-NCs were measured to assess their antibacterial potency against the Staphylococcus aureus (IZD ≈ 24 mm) and Escherichia coli (IZD ≈ 25 mm) bacterial strains. The strong UV absorption (in the range of 269 and 310 nm) shown by these NCs was established to be useful for the antibacterial drug development and food treatment.

Pretreatment Efficiency Using Autoclave High-Pressure Steam and Ultrasonication in Sugar Production from Liquid Hydrolysates and Access to the Residual Solid Fractions of Wheat Bran and Oat Hulls.

The objective of this study was to evaluate the combination of physical and chemical pretreatments of wheat bran (WB) and oat hulls (OH) to obtain fermentable sugars and a residual solid fraction with increased susceptibility to enzymatic hydrolysis. High-pressure steam in an autoclave and ultrasonication were employed as pretreatments, and for both processes, WB and OH were treated with sulfuric acid (H2SO4), neutral medium (H2O) and sodium hydroxide (NaOH). Autoclave high-pressure steam in an acid medium was the most effective for the release of sugars (total sugars, xylose and glucose) from liquid hydrolysates and for the modification of the residual solid fraction. The cellulose content of the WB residual solid fraction increased from 7.19 to 39.17%, the lignin fraction of WB decreased from 6.40 to 3.21%, the cellulose content of OH increased from 31.16 to 61.53%, and lignin fraction of OH decreased from 18.12 to 7.24%, resulting in materials more susceptible to enzymatic hydrolysis.

Behaviour of Tetrabenazine in Acid Medium: Reassessment and Impact on Formulation.

Thorough studies of previous analytical stress data of tetrabenazine, a dopamine depleting agent, showed a potential susceptibility to acidic conditions. Hence, the behavior of tetrabenazine acidic solutions was studied by LC-MS and NMR spectroscopy. Reverse-phase LC-MS analysis of tetrabenazine acidic aqueous solutions consistently showed a main lipophilic impurity in a proportion of 15 to 20%. NMR spectroscopy studies did not allow to completely ascertain its structure. However, we hypothesize an interconversion of trans-tetrabenazine with its unstable cis isomer via an open isoquinolinium intermediate. Evaluation of tetrabenazine integrity in orodispersible films was reassessed in light of these observations after formulation and during stability study. Even if interconversion of trans-tetrabenazine with its cis isomer was observed in orodispersible films containing tetrabenazine, this phenomenon seems not to have any consequences for the overall tetrabenazine bioavailability.

A simple yet sensitive colorimetric nitrite ions assay based on diazotization with p­Aminobenzoic and coupling with phloroglucinol in acidic medium.

Immoderate intake of nitrite (NO2-) is deleterious human health and may result in causing dangerous diseases. In this study, nitrite detection system was successfully fabricated based on a unique diazo-coupling reaction of p­Aminobenzoic acid (PABA) and phloroglucinol (1, 3, 5­trihydroxybenzene). Upon the presence of NO2- in an acid medium, p­Aminobenzoic acid could not only form diazonium ion easily but also couple with p­Aminobenzoic acid, and results forming yellow water-soluble azo dye that shows maximum absorption at 434 nm. Under the further accurate determination condition, such as acid concentration, amount of reagents and time required, the naked-eye detection of NO2- showed excellent selectivity in compared with some anions. Especially, diazotization and coupling reaction proposed here is very fast and control of pH and temperature are unnecessary. Moreover, the color is stable for several days and Beer's law is obeyed over a wide range. Reliable detection can be made in the range of 0.05 to 1 p.p.m. of nitrite ion. Detection limit was calculated to be 0.024 p.p.m. (0.52 µâ€¯M) by UV-visible spectroscopy and 0.05 p.p.m. (1.09 µâ€¯M) by naked-eye. By using an electrochemical method, IR, SEM, and 1HNMR, the sensing mechanism can be easily verified. More importantly the proposed method was successfully applied for the determination of nitrite in a real water sample.

Synthesis and biological evaluation of 1-amino isochromans from 2-bromoethyl benzaldehyde and amines in acid medium.

We have developed a facile and efficient synthetic route to substituted isochromans for the first time by reacting 2-(2-bromoethyl)benzaldehyde with a variety of aryl, heteroaryl amines in AcOH. The reaction is catalyst/additive free and takes place at reflux conditions with short reaction time to furnish products in good to excellent yields. All the compounds have been characterized by spectral techniques such as IR, 1H NMR and Mass etc. Synthesized compounds were evaluated for antimicrobial activity against specific bacterial like 1) Staphylococcus strains aureus 2) Bacillus subtilis 3) Escherichia coli 4) Pseudomonas aeruginosa. Compounds 3e, 3n, 3 m, 3 l, 3 k, 3j and 3b showed most potent in vitro activity against bacterial strains.

Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2SO4 solution.

Pt-CeO2 /C, Pt-TiO2 /C, and Pt-ZrO2 /C electrocatalysts were prepared by using a modified microwave-assisted polyol process. Physical characterization was performed by using XRD, TEM, and EDX analyses. The incorporation of different metal oxides increased the dispersion degree of Pt nanoparticles and reduced their diameter to 2.50 and 2.33 nm when TiO2 and ZrO2 were introduced to Pt/C, respectively. The electrocatalytic activity of various electrocatalysts was examined towards methanol oxidation in H2 SO4 solution by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Among the studied composites, Pt-ZrO2 /C was selected to be a candidate electrocatalyst for better electrochemical performance in direct methanol fuel cells.

Interactions at the mild steel acid solution interface in the presence of O-fumaryl-chitosan: Electrochemical and surface studies.

The performance of synthesised O-fumaryl-chitosan (OFC) as corrosion inhibitor for mild steel in 1M HCl has been evaluated through various studies. The initial screening by weight loss method revealed the good inhibition efficiency by the inhibitor. Thermodynamic and kinetic parameters have been calculated and discussed. The mode of adsorption is physical in nature and it follows Langmuir adsorption isotherm. Electrochemical measurements supported the inhibition of mild steel by the fumaryl derivative of chitosan. Polarisation studies provided the information that the inhibition is of mixed type. The formation of inhibitor film is assured by surface morphological studies with Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The mechanism of inhibition is derived from the Fourier-transform infrared (FTIR) spectroscopy and zero charge potential measurement. The adsorbed film is characterised using FTIR and X-ray diffraction studies (XRD).

Corrosion mitigation of N-(2-hydroxy-3-trimethyl ammonium)propyl chitosan chloride as inhibitor on mild steel.

The biopolymer N-(2-hydroxy-3-trimethyl ammonium)propyl chitosan chloride (HTACC) was synthesised and its influence as a novel corrosion inhibitor on mild steel in 1M HCl was studied using gravimetric and electrochemical experiments. The compound obtained was characterised using FTIR and NMR studies. The inhibition efficiency increased with the increase in concentration and reached a maximum of 98.9% at 500 ppm concentration. Polarisation studies revealed that HTACC acts both as anodic and cathodic inhibitor. Electrochemical impedance studies confirmed that the inhibition is through adsorption on the metal surface. The extent of inhibition exhibits a negative trend with increase in temperature. Langmuir isotherm provides the best description on the adsorption nature of the inhibitor. SEM analysis indicated the presence of protective film formed by the inhibitor on the metal surface.

A highly improved method for sensitive determination of amitriptyline in pharmaceutical formulations using an unmodified carbon nanotube electrode in the presence of sulfuric acid.

The present paper describes a novel, simple and reliable differential pulse voltammetric method for determining amitriptyline (AMT) in pharmaceutical formulations. It has been described for many authors that this antidepressant is electrochemically inactive at carbon electrodes. However, the procedure proposed herein consisted in electrochemically oxidizing AMT at an unmodified carbon nanotube paste electrode in the presence of 0.1 mol L(-1) sulfuric acid used as electrolyte. At such concentration, the acid facilitated the AMT electroxidation through one-electron transfer at 1.33 V vs. Ag/AgCl, as observed by the augmentation of peak current. Concerning optimized conditions (modulation time 5 ms, scan rate 90 mV s(-1), and pulse amplitude 120 mV) a linear calibration curve was constructed in the range of 0.0-30.0 µmol L(-1), with a correlation coefficient of 0.9991 and a limit of detection of 1.61 µmol L(-1). The procedure was successfully validated for intra- and inter-day precision and accuracy. Moreover, its feasibility was assessed through analysis of commercial pharmaceutical formulations and it has been compared to the UV-vis spectrophotometric method used as standard analytical technique recommended by the Brazilian Pharmacopoeia.