Multiphase electroextraction as a simple and fast sample preparation alternative for the digital image determination of doxorubicin in saliva.

Monitoring chemotherapeutic drugs in biological fluids is, in many cases, extremely important for dose adjustment, the maintenance of therapies, and the control of side effects. In this work, a method for determining the doxorubicin in saliva by digital image analysis (DIA) was optimised and validated. Images from a paper point were obtained using a conventional and cheap flatbed scanner at a 600 ppp resolution. The RGB data channels were obtained from the images in a region of 15 × 15 pixels around the sorbent vertex. The paper point was used as sorbent material in sample preparation using a multiphase electroextraction system. Following optimisation using a Doehlert experimental design, the method was able to simultaneously extract 66 samples in 20 min. The high selectivity of the electric field associated with the sorption capacity of the cellulosic material allowed the chemotherapy drug to be pre-concentrated and quantified in a range between 50 and 500 µg L-1 (R2 > 0.98). The method also exhibited adequate parameters (limits of detection and quantification, recovery, and precision) indicating its potential application in the monitoring of doxorubicin and similar drugs in saliva.

Cellulose cone tip as a sorbent material for multiphase electrical field-assisted extraction of cocaine from saliva and determination by LC-MS/MS.

A porous and hydrophilic sorbent material was used in an extraction system, assisted by electric fields, for the extraction of cocaine in saliva and subsequent determination by ultra-high-performance liquid chromatography associated with sequential triple quadrupole mass spectrometry (UHPLC-MS/MS). The cellulose-based material was characterized by scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. The time and voltage variables applied in the extraction process were investigated through a Doehlert experimental design, and with the best conditions found (35min and 300 V) some validation parameters were evaluated. The established working range was 1-100 µg L-1 (R2 > 0.99), and the detection and quantification limits determined were 0.3 and 0.8 µg L-1, respectively. Recoveries from 80 to 115% and coefficient of variation ≤15 and 16% for intra-day and inter-day assays, respectively, were obtained for sample concentrations of LOQ, 5, 25, and 75 µg L-1, indicating satisfactory accuracy and precision for the proposed method. In addition, the method presented no matrix effect, and the extraction efficiency was between 56 and 70%. The results showed that the material used has adequate physicochemical characteristics and can be applied as a sorbent and electrolyte support in multiphase extractions using electric fields.

Renal toxicological evaluations of sulphonated nanocellulose from Khaya sengalensis seed in Wistar rats.

Nanocellulose is currently gaining attention due to its unique properties. This attention includes its application as building blocks for developing novel functional materials, plant drug and also in drug delivery systems. However, its safety remains largely untested or less understood. Thus, sulphonated nanocellulose (KSS) was prepared from cellulose (KSC) isolated from Khaya senegalensis seed (KS). KS, KSC and KSS were characterized using Fourier transformed infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TG), particle size distribution (PSD), zeta potential and scanning electron microscopy (SEM). The impact of KSS on selected renal markers of oxidative stress, inflammation and apoptosis in Wistar rats was also investigated. Thus, male rats were randomly assigned to four groups of five animals each and were treated with KSS (0, 50, 75 and 100 mg/kg BW) for 14 days. Thereafter, biomarkers of renal oxidative damage, inflammation and immunohistochemical expressions of iNOS, COX-2, Bcl-2 and p53 were evaluated. The results revealed KSS to have crystallinity of 70.40%, it was monomodal and has a flaky surface with agglomerations. KSS had no effect on markers of kidney function and oxidative damage, although there was a generalized hypernatremia after 14 days of exposure. Lastly, KSS enhanced the antioxidant status and immunohistochemical expressions of iNOS and COX-2 in the kidney of the rats. While the biomedical applications of KSS may appear plausible, our data suggests that it could induce renal toxicity via the combined impacts of electrolyte imbalance and inflammation.

Dental glass ionomer cement reinforced by cellulose microfibers and cellulose nanocrystals.

The aim of this work was to evaluate if the addition of cellulose microfibers (CmF) or cellulose nanocrystals (CNC) would improve the mechanical properties of a commercial dental glass ionomer cement (GIC). Different amounts of CmF and CNC were previously prepared and then added to reinforce the GIC matrix while it was being manipulated. Test specimens with various concentrations of CmF or CNC in their total masses were fabricated and submitted to mechanical tests (to evaluate their compressive and diametral tensile strength,modulus, surface microhardness and wear resistance) and characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The incorporation of CmF in the GIC matrix did not greatly improve the mechanical properties of GIC. However, the addition of a small amount of CNC in the GIC led to significant improvements in all of the mechanical properties evaluated: compressive strength (increased up to 110% compared with the control group), elastic modulus increased by 161%, diametral tensile strength increased by 53%, and the mass loss decreased from 10.95 to 3.87%. Because the composites presented a considerable increase in mechanical properties, the modification of the conventional GIC with CNC can represent a new and promising dental restorative material.

Cassava starch-based films plasticized with sucrose and inverted sugar and reinforced with cellulose nanocrystals.

UNLABELLED: Bionanocomposites films of cassava starch plasticized with sucrose and inverted sugar and reinforced by cellulose nanocrystals (CNCs) were prepared by solution casting method incorporating 0.1 to 5 wt% of eucalyptus CNCs. The nanocrystals were characterized using transmission electron microscopy, whereas the bionanocomposites properties were studied using Fourier transform infrared spectroscopy, tensile measurements, water solubility, swelling behavior, and water activity (a(w)). The water resistance properties (solubility and swelling behavior) of the nanocomposites were enhanced with the addition of cellulose nanofillers. These results were explained in terms of the high crystallinity of the nanocrystals and the formation of a rigid network with the nanofillers, which provide physical barriers to the permeation of water within the hydrophilic cassava matrix. The addition of CNCs in the bionanocomposites decreases a(w) linearly, reaching values below 0.5 (for CNCs concentration higher than 4 wt%), a reference value for no microbial proliferation for food product design. The presence of small concentrations of CNCs (0.1-0.3 wt%) also effectively increased the maximum tensile strength (more than 90%) and elastic modulus (more than 400%), indicating the formation of a suitable percolation network in this concentration range. Because the cellulose nanofillers enhanced the mechanical and water stability properties of the nanocomposites, the obtained results in this work may be applied to the development of biodegradable packaging or coatings to enhance shelf life of food products. PRACTICAL APPLICATION: The main drawbacks of using starch-based polymers as packaging or coating in the food industry are their low mechanical properties and inherent water sensitivity. This study demonstrates that cellulose nanocrystals can be used to: (i) obtain better mechanical properties (increasing the tensile strength and modulus more than 90% and 400%, respectively; (ii) enhance the water stability and (iii) water activity of starch-based films. These results indicate that the obtained environmentally friendly nanocomposites in this work can be used to the development of films or coatings to enhance the shelf life of food products.

Bio-based nanocomposites obtained through covalent linkage between chitosan and cellulose nanocrystals.

Bio-based nanocomposites were obtained through covalent linkage between cellulose nanocrystals (CNCs) and the natural polymer chitosan (CH). The CNCs were first functionalized with methyl adipoyl chloride (MAC) and the reactive end groups on the surface of the CNCs were reacted with the amino groups of the CH biopolymer in an aqueous medium. The functionalized CNCs and the resulting nanocomposites were characterized using FTIR, TEM, XRD, and elemental analyses. Characterization of the functionalized CNCs showed that up to 8% of the hydroxyl groups in the nanocrystals were substituted by the MAC residue. The covalent linkage between the CNCs and CH was confirmed by FTIR spectroscopy. The nanocomposites demonstrated a significant improvement in the mechanical performance and a considerable decrease in the hydrophilicity relative to the neat chitosan. The approach used in this work can be extended to other natural polymers.

Physicochemical properties of methylcellulose and dodecyltrimethylammonium bromide in aqueous medium.

Interactions between uncharged polymers and cationic surfactants are considered weaker than interactions with the anionic analogues. This work describes the binding occurring between methylcellulose (MC) and the cationic surfactant DTAB in aqueous medium. In the absence of salt, MC-DTAB exhibits a maximum in hydrodynamic radius, R(h,slow), with the increase in the surfactant concentration. Otherwise, in presence of salt the MC-DTAB system shows only a linear increase of R(h,slow). CAC is lower than the CMC, which is taken as an evidence of binding between the cationic surfactant and neutral polymer that induces the aggregation process. Static light scattering, rheology and micro-DSC results highlight the hydrophobic MC-DTAB association. Salt-out and the salt-in effects were observed in presence of DTAB, with a clear transition at concentration values close to the CMC, as judged from rheological and micro DSC measurements. Indeed, DTAB affects both the pattern of the sol-gel transition and the gel strength.

Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan.

A new biodegradable nanocomposite was obtained from layer-by-layer (LBL) technique using highly deacetylated chitosan and eucalyptus wood cellulose nanowhiskers (CNWs). Hydrogen bonds and electrostatic interactions between the negatively charged sulfate groups on the whisker surface and the ammonium groups of chitosan were the driving forces for the growth of the multilayered films. The film growth was followed by UV-vis spectroscopy through the maximum value of the absorption band at 194 nm and showed the deposition of 14.7 mg.m(-2) of chitosan polymer in each cycle. Scanning electron microscopy showed high density and homogeneous distribution of CNWs adsorbed on each chitosan layer. Cross-section characterization of the assembled films indicates an average of approximately 7 nm of thickness per bilayer. The results presented in this work indicate that the methodology used can be extended to different biopolymers for the design of new biobased nanocomposites in a wide range of applications such as biomedical and food packaging.

Jack bean urease (EC 3.5.1.5) aggregation monitored by dynamic and static light scattering.

Aggregation of jack bean urease (JBU) is involved in many alterations of its biological properties, notably the ureolytic and entomotoxic activities. In order to investigate this phenomenon, protein aggregates were characterized by dynamic (DLS) and static light scattering (SLS) spectroscopies through determination of apparent hydrodynamic radii, the average molecular masses, radii of gyration and second virial coefficients. No effect of disulfide reducing agents on protein association was observed contrasting with previous reports implicating their function in the prevention of JBU aggregation. The influence of freeze-thawing cycles on protein aggregation was also investigated. Our results showed that after freeze-thawing cycles the native form of JBU with apparent hydrodynamic radius of 7 nm and radius of gyration of 12 nm is replaced by high-order oligomers and this aggregation is not reverted neither by dithiothreitol (DTT) treatment nor by high concentration of salts. Altogether the data help to understand the complex behavior of JBU in solution and may correlate with the diversity of biological properties of this enzyme.