Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food simulants

Adhesives used in food packaging to glue different materials can provide several substances as potential migrants, and the identification of potential migrants and migration tests are required to assess safety in the use of adhesives. Solid-phase microextraction in headspace mode and gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) and ChemSpider and SciFinder databases were used as powerful tools to identify the potential migrants in the polyurethane (PU) adhesives and also in the individual plastic films (polyethylene terephthalate, polyamide, polypropylene, polyethylene, and polyethylene/ethyl vinyl alcohol). Migration tests were carried out by using Tenax(?) and isooctane as food simulants, and the migrants were analyzed by gas chromatography coupled to mass spectrometry. More than 63 volatile and semivolatile compounds considered as potential migrants were detected either in the adhesives or in the films. Migration tests showed two non-intentionally added substances (NIAS) coming from PU adhesives that migrated through the laminates into Tenax(?) and into isooctane. Identification of these NIAS was achieved through their mass spectra, and 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione were confirmed. Caprolactam migrated into isooctane, and its origin was the external plastic film in the multilayer, demonstrating real diffusion through the multilayer structure. Comparison of the migration values between the simulants and conditions will be shown and discussed.     

Morphology of the male reproductive system and spermatozoa in Centris Fabricius, 1804 (Hymenoptera: Apidae, Centridini)

The genera Centris and Epicharis constitute the Centridini and are widely distributed in the Neotropical region. Centris is also found in the southern portion of the Neartic region, although both genera are more abundant in the humid tropical regions. To describe the structure of the male reproductive system and spermatozoa, light and transmission electron microscopy were used. The male reproductive system of Centris sp. is formed by a pair of testes, a pair of deferent ducts, a pair of seminal vesicles, a pair of accessory glands and an ejaculatory duct connected to the external genitalia, the aedeagus. In this species, testes and the pre-vesicular deferens ducts as well as the seminal vesicles are encapsulated in a single conjunctive capsule, the scrotal membrane. Each testis consists of four testicular follicles, made up of cysts with up to 64 germinative cells. Histologically, the seminal vesicles are formed by a simple cylindrical epithelium, basal membrane and muscular tunic. The spermatozoa of Centris analis, C. fuscata, C. tarsata and Centris sp. are morphologically similar. They have two easily distinguishable regions: the head and flagellum. The head is formed by the two-layer acrosome, the linear nucleus and the flagellum, the centriole adjunct, the axoneme of pattern 9+9+2 microtubules, two asymmetric mitochondrial derivatives and two accessory bodies. These Centris species share various morphological characteristics of the male reproductive system and spermatozoa with the other bees previously described, indicating that several characteristics are synapomorphic for the family Apidae. Studies on the morphology of the male reproductive system and spermatozoa in Hymenoptera have demonstrated the diversity of the information provided by these reproductive structures, which can be used in taxonomy studies and the phylogeny of this important group of insects.     

Statistical Experimental Design for Obtaining Nanocellulose from Curaua Fiber

Summary: This study focuses on the methodology to obtain nanocellulose from vegetal fibers. An experimental planning was carried out for the treatment of curaua fibers and parameters were estimated, having the concentration of H₂SO₄, hydrolysis time, reaction temperature and time of applied sonication as independent variables for further statistical analysis. According to the estimated parameters, the statistically significant effects were determined for the process of obtaining nanocellulose. With the results obtained from the thermogravimetric analysis (TGA) it was observed that certain conditions led to cellulose with degradation temperatures near or even above that of the untreated cellulose fibers. The crystallinity index (I_C) obtained after fiber treatment (by X-ray diffraction technique) was higher than that of the pure fiber. Treatments with high acid concentrations led to higher IC. After the statistical experimental design, mixtures of polypropylene with fibers prepared after different treatments were performed in a mini-extruder. It was possible to observe a sharp increase in the mechanical properties through the dynamic mechanical thermal analysis (DMTA).     

Influence of Organophilic Ammonium-Free Nanoclay Incorporation on Mechanical Properties and Biodegradability of Biodegradable Polyester

Summary: Disposal of petroleum-derived polymers is a growing global environmental problem of alarming proportions, which has increased interest in the use and production of biodegradable materials. In addition to biodegradation, investment in research and development in the nanotechnology area is also significant. This study evaluated the effect of incorporation of an organophilic nanoclay ammonium-free salt (Novaclay™) on the mechanical properties and biodegradation of a biodegradable polyester (Ecoflex®), according to ASTM G 160. Ecoflex with and without incorporated Novaclay was characterized before and after biodegradation in organically enriched soil for up to 180 days, by visual analysis, optical microscopy, weight loss, differential scanning calorimetry, dynamic mechanical analysis, mechanical testing, and scanning electron microscopy. The pure Ecoflex and the Ecoflex/Novaclay nanocomposite were partially biodegraded by the method used, and showed changes in their morphological and mechanical properties.     

Modification of hemp shiv properties using water-repellent sol–gel coatings

For the first time, the hydrophilicity of hemp shiv was modified without the compromise of its hygroscopic properties. This research focused on the use of sol–gel method in preparation of coatings on the natural plant material, hemp shiv, that has growing potential in the construction industry as a thermal insulator. The sol–gel coatings were produced by cohydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) using an acidic catalyst. Methyltriethoxysilane (MTES) was added as the hydrophobic precursor to provide water resistance to the bio-based material. Scanning electron microscopy (SEM) and focused ion beam (FIB) have been used to determine the morphological changes on the surface as well as within the hemp shiv. It was found that the sol–gel coatings caused a reduction in water uptake but did not strongly influence the moisture sorption behaviour of hemp shiv. Fourier transformed infrared (FTIR) spectroscopy shows that the coating layer on hemp shiv acts a shield, thereby lowering peak intensity in the wavelength range 1200–1800?cm^?1. The sol–gel coating affected pore size distribution and cumulative pore volume of the shiv resulting in tailored porosity. The overall porosity of shiv decreased with a refinement in diameter of the larger pores. Thermal analysis was performed using TGA and stability of coated and uncoated hemp shiv have been evaluated. Hemp shiv modified with sol–gel coating can potentially develop sustainable heat insulating composites with better hygrothermal properties.

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Simple,inexpensive mass spectrometric analyzer for thermogravimetry

A low‐cost mass spectrometer attachment for thermogravimetric analysis has been constructed from readily available commercial instruments and components. The benefits of this set‐up include excellent mass‐flow repeatability, simple design, and significantly lower adoption cost as opposed to ready‐built commercial solutions. The inclusion of an open source software package allows semi‐automated, highly simplified data analysis. The results from the instrument show excellent sensitivity for small volumes of evolved gas, as well as highly reproducible signal strengths. The GUI‐based software package provides data analysis in a way that is very intuitive and that can be easily modified to work with a broad range of TG instruments. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of a Novel Molecularly Imprinted Polyvinylimidazole/Functionalized Carbon Black Nanocomposite-based Paste Electrode for Electrochemical Sensing of Imazethapyr in Rice Samples

This paper reports the development of a simple electroanalytical method for imazethapyr (IMT) determination in rice samples based on molecularly imprinted polymer and functionalized carbon black paste electrode (MIP-fCBPE). Carbon black (CB) was functionalized by the insertion of oxygenated functional groups upon acid treatment with HNO₃ and H₂SO₄. The functionalized carbon black (fCB) presented higher performance for IMT determination than the CB without functionalization. The insertion of molecularly imprinted polyvinylimidazole (MIP-VN) in the fCBPE promoted a significant increase in the cathodic peak current even at low proportions (7.5 % w/w) due to the specific binding sites for IMT recognition. For IMT determination, DPV parameters were optimized by the Doehlert matrix applying 0.1 V for 60 s as pre-treatment in acetate buffer solution (pH 3.0) as supporting electrolyte. The proposed method showed low limit of detection (0.03 μmol L⁻¹), a wide linear range (0.10–70.00 μmol L⁻¹), and good precision in terms of repeatability of intraday measures (RSD%=3.6). The method was applied in rice samples after microwave-assisted extraction of IMT and the accuracy of the method was evaluated by addition/recovery assays (96.3–105.7 %), being statistically attested using HPLC-DAD as reference technique.     

Low field NMR for quality monitoring of 3D printed surimi from cod by-products: Effects of the pH-shift method compared with conventional washing

Implementation of three-dimensional (3D) food printing and novel analytics can reduce food waste and increase utilization of seafood by-products. Low field nuclear magnetic resonance (LF-NMR) and chemometrics were used to investigate the printability and characteristics of surimi pastes from cod by-products as affected by different processing methods (the pH-shift method vs. conventional washing), addition of salt (0, 1.5, and 3%), length of cold storage (0, 4, and 7 days) until 3D printing, and steam cooking. The analysis revealed two to three water populations in the 3D printed samples. Increasing the salt concentration induced myofibrillar swelling in the conventionally prepared surimi, whereas a more salt-induced gelling effect was observed in the pH-shift processed surimi. Cooking had a decreasing effect on the T₂₁ relaxation time and its corresponding apparent population (A₂₁), corresponding to protein denaturation and water loss during cooking. Increasing the salt concentration to 3% had a protective effect towards water exchange between the A₂₁ and A₂₃ populations in the conventionally washed samples but more subtly in the pH-shift samples. Similar trends in relaxation parameters were observed after 4 and 7 days of storage, although the intermediate population A₂₂ seemed to be most affected by the storage. Overall LF-NMR was an effective quality monitoring tool for the physicochemical changes occurring in the 3D printed surimi. The analysis showed both advantages and disadvantages of the two processing methods. However, it can clearly be concluded that increasing the salt content had a stabilizing effect on the surimi, and printing of fresh raw materials is recommended.