A new approach to ion exchange chromatography with conductivity detection for adulterants investigation in dietary supplements

The extent of adulteration of dietary supplements has significantly increased in recent years. This situation worries health authorities and requires auxiliary analytical tools for the investigation of illegal substances purposely added. Ion exchange chromatography with conductivity detection is a consolidated analytical technique for the determination of inorganic compounds in various matrices. This technique has been applied to the pharmaceutical characterization of mainly impurities and degradation products. This work presents a new approach to ion exchange chromatography as a screening method to investigate the presence of amfepramone, femproporex, sibutramine, bisacodyl and amiloride in dietary supplements advertised for weight loss. The method was optimized and validated using a Metrosep C4 100/4.0 cation exchange column. The mobile phase consisted of 1.8 mm HNO₃ containing 2% acetonitrile (v/v), with a flow rate of 0.9 ml min^?1, and nonsuppressed conductivity detection was applied. The limits of detection and quantification varied from 1.01 to 3.62 mg L^?1 and from 1.48 to 8.72 mg L^?1, respectively. The proposed method was successful applied to 78 solid dietary supplement samples, in two of which adulterations were found. Moreover, ion exchange chromatography with conductivity detection could be easily used for quality control without prior complex sample pre‐treatment.     

On a criterion for continuity and compactness of composition operators acting on α-Bloch spaces

In this Note we give a new criterion for the continuity and compactness of composition operators acting on α-Bloch spaces.     

Exploring polymer solubility with thermally-responsive Diels-Alder monomers: Revisiting the monkey's fist

Thermo-responsive monomers were designed to contain a Diels-Alder (DA) adduct such that cyclo-reversion would yield either the maleimide or the furan unit attached to the polymer chain. These thermally responsive monomers were then copolymerized with N-isopropylacrylamide (NIPAM) via reversible addition-fragmentation chain-transfer (RAFT) polymerization to yield linear gradient-copolymer structures as a comparison to existing nanogel/starlike systems to understand how polymer topology and composition influence solution-state properties. Using UV–Vis spectroscopy, it was determined that solution-state properties were thermally dependent and influenced by a number of variables such as comonomer feed ratio, polymer chain end functionality, and polymer backbone length and composition. Manipulation of the feed ratio allowed for control over the cloud point, including the breadth and location of phase separation. Thermal treatment of these copolymers revealed tunable and predictable variations in previously observed transitions, directly correlated to cleavage of the DA adducts and change in polymer backbone composition. Finally, on cooling cycles, a double sigmoid was sometimes observed, indicating a complex globule to random coil transition correlated to polymer chain end composition. These studies help understand how to untie the “monkey's fist.”     

The Catalytic Mechanism of the Retaining Glycosyltransferase Mannosylglycerate Synthase

To protect their intracellular proteins, extremophile microorganisms synthesize molecules called compatible solutes. These molecules are the result of the attachment of a small negatively charged molecule to a sugar molecule. It has been found that these molecules, not only protect the microorganism against osmotic stress but also against other extreme conditions. They can also confer protection against extreme conditions to isolated enzymes from different organisms making them an exciting prospect for potential biotechnological applications. One of the most widespread compatible solute in hyperthermophile organisms is the molecule 2-O-α-D-mannosyl-D-glycerate (MG). In addition to confer protection to proteins against extreme conditions, MG was found to prevent Alzheimer's β-amyloid aggregation and reduce α-synuclein fibril formation in Parkinson's disease. In this work we studied, using computational methods, the catalytic mechanism of the synthesis of MG by the enzyme mannosylglycerate synthase (MGS) from the thermophilic bacteria Rhodothermus marinus.     

INAA and PIXE characterization of heavy metals and rare earth elements emissions from phosphorite handling in harbours

Harbour activities such as loading, unloading and transport of materials may be an important source of Atmospheric Particulate Matter (APM). Depending on the materials, the type of operation and the meteorological conditions, these activities may have an impact on the levels of APM around harbour areas. The aim of this work was to characterize the emissions of dust providing from operations associated with phosphorite handling in harbours. Phosphorite is a non-detrital sedimentary rock which contains high amounts of phosphate bearing minerals and is used for the production of phosphorous based fertilizers. When handled in harbours frequently cause visual and environment impacts due to its physical and chemical characteristics. The techniques Instrumental Neutron Activation Analysis and Particle Induced X-ray Emission were applied as sensitive analytical tools for the determination of heavy metals and rare earth elements in phosphorite and in the APM sampled in the harbour during the unloading operations. Results showed that manipulation of phosphorite during harbour operations resulted in high emissions of particles, principally from the coarse fraction. These emissions were enriched in rare earth elements and heavy metals and were very affected by the provenience of the phosphorite.     

Advanced design of t and pH dual‐responsive PDEAEMA–PVCL core–shell nanogels for siRNA delivery

The synthesis, characterization, and potential application as gene delivery systems of biodegradable dual‐responsive core–shell nanogels based on poly(2‐diethylaminoethyl) methacrylate (PDEAEMA) and poly(N‐vinylcaprolactam) (PVCL) are reported. These core–shell nanogels, having a PDEAEMA‐based core and a PVCL‐based shell, were synthesized by batch seeded emulsion polymerization. An indepth study of their swelling behavior was carried out, which presented a dual‐dependent thermo‐ and pH sensitivity. Core–shell nanogels synthesized formed complexes spontaneously through electrostatic interactions when mixing with small interfering RNA (siRNA) molecules. Moreover, the core–shell nanogel/siRNA complexes showed higher polyanion exchange resistance compared to that of the PDEAEMA‐based nanogel/siRNA complexes, indicating that the PVCL‐based shell enhanced the stability of the complexes. In vitro siRNA release profiles showed that siRNA release was controlled by the pH of the medium as well as by the crosslinking density of the PVCL‐based shell. These results indicate that dual‐responsive core–shell nanogels synthesized could be potentially useful as gene delivery systems. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3203–3217     

Experimental Measurement and Numerical Validation of Bone Cement Mantle Strains of an In Vitro Hip Replacement Using Optical FBG Sensors

Experimental pre-clinical tests associated with numeric models of cemented implants are important for screening of new implants in the market. The aim of this study was to measure strain profiles and maximum temperature polymerization inside a cement mantle of an in vitro cemented hip reconstruction using optical fiber Bragg grating (FBG) sensors. For this purpose, a hip femoral prosthesis was instrumented with 12 FBG sensors, three in each aspect of the femur, anterior, posterior, medial and lateral. These were positioned at the proximal, middle and distal part of the cement mantle relatively to the stem. Another sensor was placed in the lateral-proximal region of the mantle to measure the maximum temperature of cement polymerization. The strains measured were compared with those obtained with a Finite Element model, both for quaistatic mechanical loading. The results show that the experimental technique used can measure strains inside the cement mantle with good correlation, R²?=?0.970, with the numerical model results. The results present a maximum temperature of polymerization around 110°C inside of cement at proximal region. It was also observed strain concentration in lateral aspect of the femur in polymerization process. The procedure hereby explained can be used to improve experimental pre-clinical tests to measure the strain distribution inside the cement mantle as well as residual strain and temperature variation along with time, as a result of the curing process of cement.