Antitumor Activity of Ionic Liquids Based on Ampicillin

Significant antiproliferative effects against various tumor cell lines were observed with novel ampicillin salts as ionic liquids. The combination of anionic ampicillin with appropriate ammonium, imidazolium, phosphonium, and pyridinium cations yielded active pharmaceutical ingredient ionic liquids (API‐ILs) that show potent antiproliferative activities against five different human cancer cell lines: T47D (breast), PC3 (prostate), HepG2 (liver), MG63 (osteosarcoma), and RKO (colon). Some API‐ILs showed IC₅₀ values between 5 and 42 nM , activities that stand in dramatic contrast to the negligible cytotoxic activity level shown by the ampicillin sodium salt. Moreover, very low cytotoxicity against two primary cell lines—skin (SF) and gingival fibroblasts (GF)—indicates that the majority of these API‐ILs are nontoxic to normal human cell lines. The most promising combination of antitumor activity and low toxicity toward healthy cells was observed for the 1‐hydroxyethyl‐3‐methylimidazolium–ampicillin pair ([C₂OHMIM][Amp]), making this the most suitable lead API‐IL for future studies.     

New Hybrid Nanomaterial Based on Self-Assembly of Cyclodextrins and Cobalt Prussian Blue Analogue Nanocubes

Supramolecular self-assembly has been demonstrated to be a useful approach to developing new functional nanomaterials. In this work, we used a cobalt Prussian blue analogue (PBA, Co₃[Co(CN)₆]₂) compound and a β-cyclodextrin (CD) macrocycle to develop a novel host-guest PBA-CD nanomaterial. The preparation of the functional magnetic material involved the self-assembly of CD molecules onto a PBA surface by a co-precipitation method. According to transmission electronic microscopy results, PBA-CD exhibited a polydisperse structure composed of 3D nanocubes with a mean edge length of 85 nm, which became shorter after CD incorporation. The supramolecular arrangement and structural, crystalline and thermal properties of the hybrid material were studied in detail by vibrational and electronic spectroscopies and X-ray diffraction. The cyclic voltammogram of the hybrid material in a 0.1 mol·L⁻¹ NaCl supporting electrolyte exhibited a quasi-reversible redox process, attributed to Co²⁺/Co³⁺ conversion, with an E_1/2 value of 0.46 V (vs. SCE), with higher reversibility observed for the system in the presence of CD. The standard rate constants for PBA and PBA-CD were determined to be 0.07 and 0.13 s⁻¹, respectively, which suggests that the interaction between the nanocubes and CD at the supramolecular level improves electron transfer. We expect that the properties observed for the hybrid material make it a potential candidate for (bio)sensing designs with a desirable capability for drug delivery.     

Different bacterial models for in vitro induction of non‐cavitated enamel caries‐like lesions: Microhardness and polarized light miscroscopy analyses

The aim of this study was to compare different bacterial models for in vitro induction of non‐cavitated enamel caries‐like lesions by microhardness and polarized light microscopy analyses. One hundred blocks of bovine enamel were randomly divided into four groups (n = 25) according to the bacterial model for caries induction: (A) Streptococcus mutans, (B) S. mutans and Lactobacillus acidophilus, (C) S. mutans and L. casei, and (D) S. mutans, L. acidophilus, and L. casei. Within each group, the blocks were randomly divided into five subgroups according to the duration of the period of caries induction (4–20 days). The enamel blocks were immersed in cariogenic solution containing the microorganisms, which was changed every 48 h. Groups C and D presented lower surface hardness values (SMH) and higher area of hardness loss (ΔS) after the cariogenic challenge than groups A and B (P < 0.05). As regards lesion depth, under polarized light microscopy, group A presented significantly lower values, and groups C and D the highest values. Group B showed a higher value than group A (P < 0.05). Groups A and B exhibited subsurface caries lesions after all treatment durations, while groups C and D presented erosion‐type lesions with surface softening. The model using S. mutans, whether or not it was associated with L. acidophilus, was less aggressive and may be used for the induction of non‐cavitated enamel caries‐like lesions. The optimal period for inducing caries‐like lesions was 8 days. Microsc. Res. Tech. 78:444–451, 2015. © 2015 Wiley Periodicals, Inc.     

Bioreduction of α‐Acetoxymethyl Enones: Proposal for an SN2′ Mechanism Catalyzed by Enereductase

(Z)‐3‐Acetoxymethyl‐4‐R‐3‐buten‐2‐ones (R=aryl, alkyl) and (Z)‐3‐methyl‐4‐R‐3‐buten‐2‐ones (R=aryl) were synthesized and submitted to reduction by the yeast Saccharomyces cerevisiae producing the (R)‐ and (S)‐4‐R‐3‐methybutan‐2‐ones, respectively. This stereochemistry control strategy was applied in the syntheses of (R)‐ and (S)‐Tropional® with moderate to high enantiomeric excesses. Other (Z)‐3‐acyloxymethyl‐4‐phenyl‐3‐buten‐2‐ones showed similar behavior to the (Z)‐3‐acetoxymethyl counterpart, and the acylated Morita–Baylis–Hillman adduct 1‐acetoxy‐2‐methylene‐1‐phenylbutan‐3‐one produced a mixture of products, with and without the acetoxy group, via three different reaction pathways. In addition to experiments employing whole cells, those in which isolated enereductases were used suggested that the main pathway through which the loss of the acetoxy group occurs during the biocatalytic cascade is an S_N2′‐type reaction, rather than formal hydrogen addition followed by acetic acid elimination. Finally, related ethyl enones were reduced enantioselectively by the yeast Candida albicans, producing both (R)‐ and (S)‐reduction products, depending on the presence of the acetoxy group in the starting material.

     

Chemical, Microbiological, and Sensory Quality of Cod Products Salted in Different Brines

ABSTRACT: Studies were carried out on the effect of different brines containing high concentrations of calcium chloride (CaCl₂, 0.8%w/w), magnesium chloride (MgCl₂, 0.4%w/w), and potassium chloride (KCl, 50%) on the chemical (chloride and moisture contents), microbial (total viable counts, total coliforms, enterococci, and staphylococci), and sensory quality of salted cod. The brines were prepared from combinations of the Ca, Mg, and K ions and sodium chloride (NaCl) at pH 6.5 and 8.5. Additionally, 3 salts (one composed solely of NaCl, another commercial sea salt from the southern Europe and, finally, a natural salt from northern Europe) were also tested. Principal component analysis structured the chemical and microbiology data in 3 clusters: (1) an extreme cluster, formed by cod brined in the commercial sea salt, which achieved the highest microbiological counts, namely 4.1 log CFU/g on plate count agar (PCA) and 1250 coliforms/g; (2) an intermediate cluster composed of cod salted in brine containing 50% NaCl, 0.4% MgCl₂, and 49.6% KCl (pH 6.5); and (3) a central cluster, including all the other treatments, which presented the lowest microbiological counts, namely 2.4 log CFU/g on PCA and 20 coliforms/g. Although the batches of the intermediate cluster presented slightly higher total viable and staphylococci counts than the central cluster, the presence of Mg and K ions improved the color of the salted product. In the assayed concentrations, CaCl₂, MgCl₂, and KCl can be used in the brining of cod without adversely affecting the microbiological and sensory quality of the salted cod.     

DETERMINATION OF DIACETYL IN BEER USING DIFFERENTIAL-PULSE POLAROGRAPHY

A Polarographie method is proposed for the determination of diacetyl and other vicinal diketones in beer. Similar to the EBC official spectrophotometric method, diacetyl is derivatised with o-phenylene-diamine, producing 2,3-dlmethylquinoxaline, a polarographically active compound . The Polarographic method allows discrimination between diacetyl and methylglyoxal and a detection limit ten times lower than the EBC method is obtained. In addition, problems of erratic results for diacetyl may be avoided and data are in good agreement with those obtained by gas chromatography with electron capture detection and headspace sampling . It is suggested that high results obtained with the spectrophotometric method may be attributed to an erroneous procedure used in the spectrophotometric calculations. An alternative procedure is proposed, with which lower values for diacetyl in beer are obtained, similar to those found with other methods. These low diacetyl values are near the detection limit of the spectrophotometric method .     

Investigating the cutting phenomena in free-form milling using a ball-end cutting tool for die and mold manufacturing

This paper presents an investigation of nonplanar tool-workpiece interactions in free-form milling using a ball-end cutting tool, a technique that is widely applied in the manufacturing of dies and molds. The influence of the cutting speed on the cutting forces, surface quality of the workpiece, and chip formation was evaluated by considering the specific alterations of the contact between tool-surface along the cutting time. A trigonometric equation was developed for identifying the tool-workpiece contact along the toolpath and the point where the tool tip leaves the contact with the workpiece. The experimental validation was carried out in a machining center using a carbide ball-end cutting tool and a workpiece of AISI P20 steel. The experimental results demonstrated the negative effect of the engagement of the tool tip into the cut on machining performance. The length of this engagement depends on the tool and workpiece curvature radii and stock material. When the tool tip center is in the cut region, the material is removed by shearing together with plastic deformation. Such conditions increase the cutting force and surface roughness and lead to an unstable machining process, what was also confirmed by the chips collected.     

Sorption‐Enhanced Steam Reforming of Ethanol: Thermodynamic Comparison of CO2 Sorbents

A thermodynamic analysis is performed with a Gibbs free energy minimization method to compare the conventional steam reforming of ethanol (SRE) process and sorption‐enhanced SRE (SE‐SRE) with three different sorbents, namely, CaO, Li₂ZrO₃, and hydrotalcite‐like compounds (HTlc). As a result, the use of a CO₂ adsorbent can enhance the hydrogen yield and provide a lower CO content in the product gas at the same time. The best performance of SE‐SRE is found to be at 500 °C with an HTlc sorbent. Nearly 6 moles hydrogen per mole ethanol can be produced, when the CO content in the vent stream is less than 10 ppm, so that the hydrogen produced via SE‐SRE with HTlc sorbents can be directly used for fuel cells. Higher pressures do not favor the overall SE‐SRE process due to lower yielding of hydrogen, although CO₂ adsorption is enhanced.     

Assessment of production efficiency,physicochemical properties and storage stability of spray-dried propolis,a natural food additive,using gum Arabic and OSA starch-based carrier systems

The aim of this work was to obtain propolis in a powder, alcohol-free, water-dispersed and shelf-stable form. Propolis extract was spray-dried using gum Arabic and octenyl succinic anhydride (OSA) starch as carriers in two different weight ratios (1:4 and 1:6). Spray-dried propolis samples were evaluated for morphology, moisture, water activity, water dispersibility, hygroscopicity, particle size, particle distribution, entrapping efficiency, stability, isotherms and antioxidant properties. The spray-drying process produced round particles with sizes ranging from 15 to 24 μm. This process preserved the antioxidant activity of propolis and also allowed propolis to be obtained in a powder form, which was stable during storage at room temperature, had low hygroscopicity and was highly dispersible in cold water. The application of this technology could increase the use of propolis in various industrial applications, such as an antimicrobial and as an antioxidant in food.