Solubility In Aqueous Solutions Research Articles

Benchmark Dose Modeling Approaches for Volatile Organic Chemicals Using a Novel Air-Liquid Interface In Vitro Exposure System.

Inhalation is the most relevant route of volatile organic chemical (VOC) exposure; however, due to unique challenges posed by their chemical properties and poor solubility in aqueous solutions, in vitro chemical safety testing is predominantly performed using direct application dosing/submerged exposures. To address the difficulties in screening toxic effects of VOCs, our cell culture exposure system permits cells to be exposed to multiple concentrations at air-liquid interface (ALI) in a 24-well format. ALI exposure methods permit direct chemical-to-cell interaction with the test article at physiological conditions. In the present study, BEAS-2B and primary normal human bronchial epithelial cells (pHBEC) are used to assess gene expression, cytotoxicity, and cell viability responses to a variety of volatile chemicals including acrolein, formaldehyde, 1,3-butadiene, acetaldehyde, 1-bromopropane, carbon tetrachloride, dichloromethane, and trichloroethylene. BEAS-2B cells were exposed to all the test agents, whereas pHBECs were only exposed to the latter 4 listed above. The VOC concentrations tested elicited only slight cell viability changes in both cell types. Gene expression changes were analyzed using benchmark dose (BMD) modeling. The BMD for the most sensitive gene set was within one order of magnitude of the threshold-limit value reported by the American Conference of Governmental Industrial Hygienists, and the most sensitive gene sets impacted by exposure correlate to known adverse health effects recorded in epidemiologic and in vivo exposure studies. Overall, our study outlines a novel in vitro approach for evaluating molecular-based points-of-departure in human airway epithelial cell exposure to volatile chemicals.

In Vivo Investigation of (2-Hydroxypropyl)-β-cyclodextrin-Based Formulation of Spironolactone in Aqueous Solution for Paediatric Use.

Spironolactone (SPL), a potent anti-aldosterone steroidal drug used to treat several diseases in paediatric patients (e.g., hypertension, primary aldosteronism, Bartter’s syndrome, and congestive heart failure), is not available in child-friendly dosage forms, and spironolactone liquids have been reported to be unpalatable. Aiming to enhance SPL solubility in aqueous solution and overcome palatability, herein, the effects of (2-hydroxypropyl)-β-cyclodextrin (HP-β-CyD) were thoroughly investigated on solubilisation in water and on masking the unpleasant taste of SPL in vivo. Although the complexation of SPL with HP-β-CyD was demonstrated through phase solubility studies, Job’s plot, NMR and computational docking studies, our in vivo tests did not show significant effects on taste aversion. Our findings, on the one hand, suggest that the formation of an inclusion complex of SPL with HP-β-CyD itself is not necessarily a good indicator for an acceptable degree of palatability, whereas, on the other hand, they constitute the basis for investigating other cyclodextrin-based formulations of the poorly water-soluble steroidal drug, including solid dosage forms, such as spray-dried powders and orodispersible tablets.

Physicochemical Profile of Antiandrogen Drug Bicalutamide: Solubility, Distribution, Permeability.

The pharmacologically relevant physicochemical properties of the antiandrogen drug bicalutamide (BCL) have been determined for the first time. Solubility in aqueous solution, 1-octanol, n-hexane, and ethanol was measured by the shake flask method in the temperature range of 293.15–313.15 K. The compound was shown to be poorly soluble in aqueous medium and n-hexane; at the same time, an essentially higher solubility in the alcohols was revealed. The following order of molar solubility was determined: ethanol > 1-octanol > water ≈ n-hexane. The solubility was correlated with the Van’t Hoff and Apelblat equations. Evaluation of the Hansen solubility parameters and the atomic group contribution approach of Hoftyzer and Van Krevelen demonstrated consistency with the experimental data and good potential adsorption of bicalutamide. The temperature dependences of the distribution coefficients in the 1-octanol/water and n-hexane/water two-phase systems were measured and discussed in the framework of the thermodynamic approach. The ∆logD parameter determined from the distribution experiment clearly demonstrated the preference of the lipophilic delivery pathways for the compound in the biological media. The overall thermodynamic analysis based on the solubility and distribution results of the present study and the sublimation characteristics published previously has been performed. To this end, the thermodynamic parameters of the dissolution, solvation, and transfer processes were calculated and discussed in view of the solute-solvent interactions. The permeation rate of BCL through the PermeaPad barrier was measured and compared with PAMPA permeability.

Structure-Photoreactivity Relationship of 3-Hydroxyflavone-Based CO-Releasing Molecules.

Carbon monoxide (CO) is an endogenous signaling molecule that regulates diverse physiological processes. The therapeutic potential of CO is hampered by its intrinsic toxicity, and its administration poses a significant challenge. Photoactivatable CO-releasing molecules (photoCORMs) are an excellent tool to overcome the side effects of untargeted CO administration and provide precise spatial and temporal control over its release. Here, we studied the CO release mechanism of a small library of derivatives based on 3-hydroxy-2-phenyl-4H-benzo[g]chromen-4-one (flavonol), previously developed as an efficient photoCORM, by steady-state and femto/nanosecond transient absorption spectroscopies. The main objectives of the work were to explore in detail how to enhance the efficiency of CO photorelease from flavonols, bathochromically shift their absorption bands, control their acid-base properties and solubilities in aqueous solutions, and minimize primary or secondary photochemical side-reactions, such as self-photooxygenation. The best photoCORM performance was achieved by combining substituents, which simultaneously bathochromically shift the chromophore absorption spectrum, enhance the formation of the productive triplet state, and suppress the singlet oxygen production by shortening flavonol triplet-state lifetimes. In addition, the cell toxicity of selected flavonol compounds was analyzed using in vitro hepatic HepG2 cells.

Surfactant Adsorption to Gypsum Surfaces and the Effects on Solubility in Aqueous Solutions.

Vibrational sum frequency generation (VSFG) spectroscopy, conductometric titration measurements, and EDX elemental mapping were used to examine surfactant adsorption to the gypsum (010) surface and assess the effects of surfactant adsorption on gypsum solubility in aqueous solutions. Sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium chloride (DTAC) were used as anionic and cationic surfactants, respectively. Gypsum/SDS interactions result in an ordered precipitate layer on the gypsum surface after water evaporation; gypsum/DTAC interaction did not show a similar effect, despite exposure of gypsum to equivalent amounts of surfactant. VSFG spectra showed that SDS molecules adsorb with their chains parallel to the gypsum surface; spectra from gypsum surfaces treated with DTAC, however, showed no measurable response, implying that these surfactants form disorganized aggregates with no polar ordering. Vibrational data were supported by independent EDX measurements that show a uniform distribution of SDS across the gypsum surface. In contrast, element-specific EDX images showed that DTAC clustered in tightly localized patches that left most of the gypsum surface exposed. The uniform adsorption of SDS on the gypsum surface suppresses long-term dissolution up to 40% when compared to samples exposed to DTAC. Gypsum samples in DTAC-containing solutions lose approximately the same amount of material to dissolution as samples immersed in pure water.

Influence of Air Solubility on the Flotation Performance of Low-Rank Coal.

Low-rank coal (LRC) contains large amounts of harmful impurities that must be processed before utilization. Flotation is an effective means for separating fine particles, which can be influenced by air solubility in water. In this work, deaerated water (DW), ordinary water (OW), and pressurized water (PW) were prepared to research the underlying mechanism of the effect of air solubility on the flotation performance of LRC. The results show that PW dissolves the greatest amount of air in the three kinds of water (DW, OW, and PW). The flotation performance of LRC in different water types is directly proportional to air solubility in aqueous solutions. In addition, the induction time of LRC in PW (600 ms) is significantly shorter than those in OW (1200 ms) and DW (4000 ms). Atomic force microscopy (AFM) studies reveal that typical interfacial nanobubbles (NBs) only form on a highly oriented pyrolytic graphite (HOPG) surface in PW due to the supersaturated air in water. Furthermore, the interaction between LRC particles and HOPG in PW is significantly stronger than those in both OW and DW, which is attributed to the capillary force of rgw nanobubble bridge formed between particles. The hydrophobic interaction enhanced by NBs is critically important for the attachment of LRC particles to macrobubbles in flotation. Overall, air solubility in water has a great effect on LRC flotation performance, and PW flotation technology can be extended to LRC purification.

Water-Soluble Porphyrin-Based Nanoparticles Derived from Electrostatic Interaction for Enhanced Photodynamic Therapy

Pyrrole and porphyrin-derived nanoparticles have great potential use in bioimaging and therapy because of their unique magnetic, optical, and other photophysical properties, whereas the poor solubility in aqueous solution is one of the drawbacks of current photosensitizers for their photodynamic therapy (PDT) applications. Here, we developed a kind of water-soluble porphyrin-based nanoparticles that are coassembled mainly by the electrostatic interaction of anionic porphyrins and cationic tetraphenylmethane derivative. No aggregation-caused quenching (ACQ) was detected for these nanoparticles. In addition, the simple porphyrin transformation into nanoparticles improved their ability to generate reactive oxygen species singlet oxygen (1O2), which is an important factor causing apoptosis. The coassembled water-soluble porphyrin-based nanoparticles exhibited enhanced antitumor efficiency via PDT both in vitro and in vivo.

Targeted delivery of cancer drug paclitaxel to chordomas tumor cells via an RNA nanoparticle harboring an EGFR aptamer

Paclitaxel has been extensively used in clinics for cancer treatment. However, its limited solubility in aqueous solution and high occurrence of side effects have also been widely reported. In this study, we constructed a biocompatible RNA nanoparticle delivery system (3WJ-EGFRapt) that includes 3WJ (3-way junction) nanoparticle with a size of 4.85 ± 0.59 nm as a backbone and an EGFR (epidermal growth factor receptor) aptamer for specific targeting to chordomas cells, which owns the encapsulation ability of drug paclitaxel (PTX) for cancer therapy. Confocal microscopy and flow cytometry results confirmed 3WJ-EGFRapt nanoparticle exhibited excellent specific targeting to chordomas cell U-CH2 which is an EGFR(+) cell line; while the 3WJ nanoparticle lose the targeted ability. Both of the two nanoparticles own no sensitivity to lung cancer cell H520 which is an EGFR(-) cell line. Moreover, the 3WJ-EGFRapt nanoparticle encapsulated drug PTX could enhance the inhibition efficiency of chordomas tumor cells U-CH2 as compared to free PTX alone. This work demonstrates that RNA-3WJ constructed with a targeting aptamer provides a compromising targeted drug delivery ability on chordomas cells for therapeutics.

Interfacial Microextraction Boosting Nitrogen Feed for Efficient Ambient Ammonia Synthesis in Aqueous Electrolyte

AbstractThe extremely low nitrogen (N2) solubility in aqueous solution greatly limits the gas reactant supply to catalysts resulting in a bottleneck in establishing efficient electrocatalytic N2 reduction reaction (NRR). Here, aiming at fairly few N2 dissolving in aqueous electrolyte, an N2‐microextractor (NME) that can extract the N2 from water, then feed it to catalysts on electrodes, is reported. The NME consists of polymer framework and extractant that possess high solubility for N2, which serves as an ultra‐thin interfacial system wrapping around electrodes. As expected, the enhancement of N2 supply in NRR leads to a record‐high Faradaic efficiency (80.1%) with an ammonia yield rate of 58.3 µg h−1 mg−1 under ambient conditions. This is of great significance to a sustainable “Ammonia Economy.”

Extending the application potential of capillary electrophoresis/frontal analysis for drug-plasma protein studies by combining it with mass spectrometry detection.

CE/frontal analysis (CE/FA) is probably one of the most frequently used modes of CE for studying affinity interactions. It is typically performed with classic UV-Vis detection that suffers from low concentration sensitivity. To overcome this limitation, the applicability of CE/FA in combination with ESI-MS detection for the investigation of drug-HSA interactions was demonstrated. The developed new method combines the advantages of CE/FA, such as low sample consumption and no labeling or immobilization of interacting partners, with the benefits of MS detection, such as higher selectivity and sensitivity; moreover, it can be used for molecules lacking a fluorophore or chromophore. The binding parameters of tolbutamide (TL) and glimepiride (GLP), first- and second-generation antidiabetics that differ strongly in their solubility in aqueous solutions, were investigated by this CE/FA-MS method. This method, in contrast to the CE/FA method with the most commonly used UV-Vis detection, is more sensitive; an almost three times lower LOD was reached. The binding parameters of TL and GLP were investigated by this CE/FA-MS method and compared with the literature data. The binding constant value of TL obtained by UV-Vis detection was lower than the value obtained by the method hyphenated with MS detection, which is probably given by the influence of the ESI parameters on the stability of drug-HSA complex. In addition, the ratio of TL and HSA concentrations was divergent in both of the experimental approaches. Finally, it can be concluded that both detection methods have their strengths and weaknesses.

Tailoring the dissolution rate and in vitro cell response of silicon nitride coatings through combinatorial sputtering with chromium and niobium.

Ceramic coatings have been widely investigated as a means to reduce wear and metallic ion release from joint implants. Silicon nitride-based coatings have been a topic of interest specifically due to their solubility in aqueous solutions. This could imply a reduced adverse immune response since the generated debris would dissolve. However, there are concerns regarding the dissolution rate and adhesion of these silicon nitride-based coatings. This study attempts to address the concern of dissolution rate as well as coating adhesion of silicon nitride coatings. We hypothesized that alloying with chromium and niobium would affect the adhesion, dissolution rate, and the resulting ion release and cell response to the coatings. A combinatorial approach was used to deposit sputtered coatings with compositional gradients both with and without a CrN interlayer. Compositional gradients were achieved for all the investigated elements: Si (38.6-46.9 at%), Nb (2.2-4.6 at%) and Cr (1.9-6.0 at%). However, while the presence of an interlayer reduced the delamination during adhesion testing, the differences in composition in the top coating did not affect the adhesion. Nor did the top coating's composition affect the surface roughness or the coatings' inherent mechanical properties (elastic modulus and hardness). All coating compositions were associated with a low Co release from the underlying metal and points with a higher Cr content (4.3-6.0 at%) gave an overall lower release of Si, Cr and Nb ions, possibly due to the formation of a stable oxide, which reduced the dissolution rate of the coating. Optimum chromium contents were furthermore found to give an enhanced in vitro fibroblast cell viability. In conclusion, the results indicate a possibility to tailor the ion release rate, which lends promise to further investigations such as tribocorrosive tests towards a future biomedical application.

Effect of a cis-4-aminopiperidine-3-carboxylic acid (cis-APiC) residue on mixed-helical folding of unnatural peptides.

The α/β-peptide 11/9-helix and the β-peptide 12/10-helix belong to "mixed" helices, in which two types of hydrogen bonds with opposite directionality alternate along the helical axis. cis-2-Aminocyclohexanecarboxylic acid (cis-ACHC) is known to promote these mixed helices and stabilize the helical propensity more than other acyclic β-residues. Application of a mixed-helical backbone still requires sufficient solubility in aqueous solution. In this regard, we chose cis-4-aminopiperidine-3-carboxylic acid (cis-APiC) as a foldamer building block that can provide both sufficient aqueous solubility and mixed-helical propensity. Conformational analyses of α/β- and β-peptides containing a cis-APiC residue by circular dichroism spectroscopy and single-crystal X-ray crystallography suggest that the incorporation of cis-APiC instead of cis-ACHC can enhance the aqueous solubility of the mixed-helical peptides without any adverse effect on helical folding. In addition, the ratio between right- and left-handed 12/10-helices of β-peptides can be rationalized by relative energies between the local conformations of the cis-APiC residue.

Comparative study on in vitro release kinetics of Gallic acid β Cyclodextrin complex and Gallic acid Pluronic loaded films

Drug delivery is one of the critical attributes that influences drug’s action in body and its effectiveness. There are various kinds of drug delivering systems that are a part of drug formulation. One such kind is the encapsulation and matrix-based drug delivering systems. Despite delivering the drug into the site of action, these drug deliverers are involved in aiding solubility, stability and bioavailability of the drug that makes it an effective one. Gallic acid, a polyphenol present in a variety of plants is a potent antioxidant. But its availability in the biological system (bioavailability) is such that it gets excreted quickly and has low solubility in aqueous solutions. Gallic acid has been encapsulated and fabricated into hydrogels. Different types of encapsulation and matrix-based delivery systems and its effectiveness are brought into light for the controlled release of Gallic Acid. Many polymer films have been tested to study release kinetics and entrapment efficiency. This paper deals with a comparative study on the in vitro release of Gallic acid - β Cyclodextrin and Gallic acid – Pluronic when loaded in Poly Vinyl Alcohol (PVA) films. Physical characteristics like tensile strength and thickness of the GA complex loaded films were determined. The free radical scavenging activity, nitric oxide scavenging activity of gallic acid complex was determined. The lipid peroxidation inhibition of these complexes was analyzed. In addition to these assays, the Gallic acid complexation characteristics were studied using Particle Size Analyzer and FTIR.

Cationic Fluoropolyphosphazenes: Synthesis and Assembly with Heparin as a Pathway to Hemocompatible Nanocoatings

The development of state-of-the-art blood-contacting devices can be advanced through integrating hemocompatibility, durability, and anticoagulant functionalities within engineered nanoscale coatings. To enable all-aqueous assembly of nanocoatings combining omniphobic fluorinated features with the potent anticoagulant activity of hydrophilic heparin, two fluoropolymers containing cationic functionalities were synthesized─poly[(trifluoroethoxy)(dimethylaminopropyloxy)phosphazene], PFAP-O, and poly[(trifluoroethoxy)(dimethylaminopropylamino)phosphazene], PFAP-A. Despite a relatively high content of fluorinated pendant groups─approximately 50% (mol) in each─both polymers displayed solubility in aqueous solutions and were able to spontaneously form stable supramolecular complexes with heparin, as determined by dynamic light scattering and asymmetric flow field-flow fractionation methods. Heparin-containing coatings were then assembled by layer-by-layer deposition in aqueous solutions. Nanoassembled coatings were evaluated for potential thrombogenicity in three important categories of in vitro tests─coagulation by thrombin generation, platelet retention, and hemolysis. In all assays, heparin-containing fluoro-coatings consistently displayed superior performance compared to untreated titanium surfaces or fluoro-coatings assembled using poly(acrylic acid) in the absence of heparin. Short-term stability studies revealed the noneluting nature of these noncovalently assembled coatings.

Amphiphilic Thermoresponsive Poly(Hydroxyaminoethers) as Effective Emulsifiers for Preparation of Waterborne Epoxy Resins

AbstractAmphiphilic poly(hydroxyaminoethers) (PHAEs) with thermoresponsive solubility in aqueous solutions are developed in this study. Through the control of stoichiometric ratios of functional groups and the reaction temperature, a series of PHAEs with different hydrophilic segments is synthesized, as evidenced by proton nuclear magnetic resonance (1H‐NMR) and Fourier transform infrared (FT‐IR) spectroscopy. These PHAEs could be dissolved in aqueous solutions and exhibit the thermal phase transitions with lower critical solution temperatures (LCSTs) due to the hydrogen bonding between the hydrophilic segments and water, as confirmed by differential scanning calorimetry (DSC). In addition, the hydrophilic‐lipophilic balance (HLB) values suggest that the PHAEs are more hydrophilic amphiphiles and suitable for use as oil‐in‐water emulsifiers. Consequently, commercially available epoxy resins can be successfully stabilized by the PHAEs in water to form stable emulsions. These crosslinkable waterborne epoxy resins show good thermal and resistance properties, and the feasibility in anticorrosion coating applications for steel surfaces is demonstrated.

A simplified semi-empirical model for modeling of CO2 solubilities in aqueous MDEA and MEA solutions

A simplified semi-empirical model was developed for modeling of carbon dioxide (CO2) solubility in aqueous solutions of methyldiethanolamine (MDEA) and monoethanolamine (MEA) with a temperature range from 283.15 K to 393.15 K, and alkanolamine molarity (1–5) mol/L. This model accounts for chemical equilibria in the liquid phase and physical equilibria between the liquid and vapor phases, which can calculate the vapor liquid equilibria (VLE) of MDEA+H2O+CO2 system and MEA+H2O+CO2 system. This paper proposes a Simplified Kent-Eisenberg Model (SKEM) to describe the chemical equilibria in amine – acid system, which is built with the conception of ion pairs meets the like-ion repulsion assumption and the local electroneutrality assumption. In the physical equilibria, the Henley coefficient was refitted using a new correlation, which was built with the combinations of sines and cosines. Adjustable parameters of the SKEM model, representing chemical equilibrium constant including activity coefficients, were determined by data regression with 187 sets of data of MDEA+H2O+CO2 system and MEA+H2O+CO2 system. The SKEM model has a good predictive ability, the Absolute Average Relative Deviations (AARD) of predicted results of SKEM model in MDEA+H2O+CO2 system and MEA+H2O+CO2 systems are 13.66% and 8.33%, respectively.

Graphene oxide decorated with fullerenol nanoparticles for highly efficient removal of Pb(II) ions and ultrasensitive detection by total-reflection X-ray fluorescence spectrometry

• Superior nanoadsorbent for highly effective adsorption of Pb(II) ions. • Impressive adsorption capacity and selectivity of the adsorbent toward Pb(II). • Extremely small adsorbent dosage and very short adsorption time. • Very low detection limit of 2.3 pg mL −1 using a benchtop TXRF instrument. • Simple and accurate analysis of complex matrix samples. In this paper, the graphene oxide (GO) decorated with fullerenol nanoparticles C 60 (OH) 22 has been designed for the highly selective separation and ultrasensitive determination of lead ions. The grafting fullerenol nanoparticles to the surface of GO solves the problem of their high solubility in aqueous solutions and simultaneously uses their high hydrophilicity and deprotonation ability. The research has revealed unique adsorption properties of GO-C 60 (OH) 22 toward Pb(II) ions at pH 5.5, i.e., minimal adsorbent dose (5 mg L −1 ), impressive resistance to ionic strength (up to 1 mol L −1 ), and enormous adsorption capacity (1307 mg g −1 ), much higher than those of any of the currently reported sorbents. The adsorption isotherms, kinetics, and effect of ionic strength indicate that an inner-sphere model based on surface complexation is the main mechanism of Pb(II) adsorption on GO-C 60 (OH) 22 . The high-resolution O1s and Pb4f X-ray photoelectron spectra confirm the strong chelation of Pb(II) ions and suggest the various coordination of Pb(II) ions to the oxygen functional groups. The exceptional properties of GO-C 60 (OH) 22 , including the possibility of application in micro-quantities, were the basis for the development of the method for ultra-sensitive detection of Pb(II) ions using such micro-analytical technique as total-reflection X-ray fluorescence spectrometry (TXRF). The method allows obtaining an extremely low detection limit of 2.3 pg mL −1 using a low-power TXRF instrument. Due to the impressive selectivity of the method, the ultra-trace Pb(II) ions can be highly accurately determined in complex matrix samples, including high salinity waters challenging to analyze using other analytical techniques.

Measurement and Thermodynamic Modeling for CO2 Solubility in the N-(2-Hydroxyethyl) Piperazine + Water System

Amine scrubbing is the most important technique for capturing CO2. The cyclic diamine N-(2-Hydroxyethyl)-piperazine (HEPZ), a derivative of piperazine, with good mutual solubility in aqueous solution, a low melting point, and a high boiling point, has the potential to replace PZ as an activator added in the mixed amine system to capture CO2. In this study, the solubility of CO2 in aqueous HEPZ solutions was determined for three HEPZ concentrations and four temperatures. The VLE data for HEPZ-H2O were obtained using a gas–liquid double circulation kettle at pressure 30–100 kPa, and the thermodynamic model for the HEPZ-H2O-CO2 system was built in Aspen Plus based on the electrolytic non-random two-liquid (ENRTL) activity model. The physical parameters for HEPZ and the interaction parameters for ENRTL, along with reaction constants of carbamate reactions, were regressed. Using the thermodynamic model, the CO2 cyclic capacity, speciation with loading, and heat of reaction for the CO2 capture system by the aqueous HEPZ solution are predicted and analyzed.

Barnase-Barstar Pair: Contemporary Application in Cancer Research and Nanotechnology.

Barnase is an extracellular ribonuclease secreted by Bacillus amyloliquefaciens that was originally studied as a small stable enzyme with robust folding. The identification of barnase intracellular inhibitor barstar led to the discovery of an incredibly strong protein-protein interaction. Together, barnase and barstar provide a fully genetically encoded toxin-antitoxin pair having an extremely low dissociation constant. Moreover, compared to other dimerization systems, the barnase-barstar module provides the exact one-to-one ratio of the complex components and possesses high stability of each component in a complex and high solubility in aqueous solutions without self-aggregation. The unique properties of barnase and barstar allow the application of this pair for the engineering of different variants of targeted anticancer compounds and cytotoxic supramolecular complexes. Using barnase in suicide gene therapy has also found its niche in anticancer therapy. The application of barnase and barstar in contemporary experimental cancer therapy is reflected in the review.

Beneficial Effects of Cerium Addition to Sulfide Inclusions on Pitting Corrosion Resistance of Stainless Steels

The pit initiation sites for commercial stainless steels have been attributed to sulfide inclusions such as MnS. The chemical composition of the inclusions affects the pitting corrosion resistance of stainless steels. It is known that the inclusion solubility in aqueous solutions affects pitting corrosion resistance. The dissolution of sulfide inclusions produces S species and exposes the bare surface of the steel matrix, resulting in high pitting susceptibility near the inclusions.1 Cerium is expected to be an additive element for insolubilizing water-soluble inclusions because Ce tends to form sulfides and Ce-sulfides exhibit low solubility in aqueous solutions. Additionally, Ce ions have been shown to be effective in the corrosion inhibition of stainless steel. In this study, a microelectrochemical technique was applied to analyze the effect of Ce addition to sulfide inclusions on the pitting corrosion resistance of stainless steels.2,3 To analyze the effect of Ce addition on water solubility of CaS inclusions, spark plasma sintering was used in the facile fabrication of stainless steel specimens containing artificial Ce-added and Ce-free inclusions.3,4,5 The pit initiation resistance at the Ce-added CaS inclusions was higher than that at the Ce-free CaS inclusions. The surface of the Ce-free CaS inclusions largely dissolved during immersion in 0.1 M NaCl, while a large part of the Ce-added CaS inclusions remained undissolved. Thermodynamic calculation showed that CeS is less soluble than CaS.To analyze the effect of Ce ions on pitting at sulfide inclusions, a type 304 stainless steel (Fe-18Cr-8Ni-1.5Mn-0.02S) was prepared by vacuum induction melting. Manganese sulfide inclusions existed in the specimens. Polarization curves were measured in 3 M NaCl and 2.97 M NaCl-0.01 M CeCl3. Pitting occurred at the MnS inclusions in the Ce3+-free solution, whereas no stable pit was generated in the Ce3+-containing solution even when metastable pitting events were observed.It was found that Ce addition inhibits the dissolution of water-soluble inclusions and improved pitting corrosion resistance. Moreover, the Ce3+ ions are expected to inhibit the pitting even after the dissolution of Ce-added inclusions.