Application of segmented analysis via multivariate curve resolution with alternating least squares to 1H-nuclear magnetic resonance spectroscopy to identify different sugar sources.

The different types of sugar employed in the food industry exhibit chemical similarity and are mostly dominated by sucrose. Owing to the sugar origin of and differences in production, the presence of certain minor organic compounds differs. To differentiate between sugars based on their botanical source, geographical origin, or storage conditions, commercial brown sugars and sugar beet extracts were analyzed by 1H NMR spectroscopy applying a segmented analysis by means of multivariate curve resolution-alternating least squares (MCR-ALS). Principal component analysis and partial least squares-discriminant analysis yielded excellent differentiation between sugars from different sources after the application of this preprocessing strategy; without loss of chemical information and with direct interpretation of the results. By applying a segmented analysis via MCR-ALS to 1H NMR sugar data, similar spectroscopic profiles could be differentiated. This improved the selectivity of 1H NMR spectroscopy for sugar source differentiation which can be useful for industrial sugar authentication purposes.

Classification and quantification of sucrose from sugar beet and sugarcane using optical spectroscopy and chemometrics.

Sucrose, obtained from either sugar beet or sugarcane, is one of the main ingredients used in the food industry. Due to the same molecular structure, chemical methods cannot distinguish sucrose from both sources. More practical and affordable methods would be valuable. Sucrose samples (cane and beet) were collected from nine countries, 25% (w/w) aqueous solutions were prepared and their absorbances recorded from 200 to 1380 nm. Spectral differences were observable in the ultraviolet-visible (UV-Vis) region from 200 to 600 nm due to impurities in sugar. Linear discriminant analysis (LDA), classification and regression trees, and soft independent modeling of class analogy were tested for the UV-Vis region. All methods showed high performance accuracies. LDA, after selection of five wavelengths, gave 100% correct classification with a simple interpretation. In addition, binary mixtures of the sugar samples were prepared for quantitative analysis by means of partial least squares regression and multiple linear regression (MLR). MLR with first derivative Savitzky-Golay were most acceptable with root mean square error of cross-validation, prediction, and the ratio of (standard error of) prediction to (standard) deviation values of 3.92%, 3.28%, and 9.46, respectively. Using UV-Vis spectra and chemometrics, the results show promise to distinguish between the two different sources of sucrose. An affordable and quick analysis method to differentiate between sugars, produced from either sugar beet or sugarcane, is suggested. This method does not involve complex chemical analysis or high-level experts and can be used in research or by industry to detect the source of the sugar which is important for some countries' agricultural policies.

Distributional homogeneity and penetration depth assessment of antibiotic added by surface coating to pellets with mid Infrared imaging and multivariate curve resolution.

Fourier Transform Mid Infrared with Attenuated Total Reflection Imaging (FTIR-ATR imaging) and Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) were used in a multiblock fashion to study the presence, distribution and penetration depth of very low concentrations of florfenicol (FF) in a complex matrix like feed pellets for salmonids. Images from the surface, at 150 µm deep and 200 µm deep from the surface were analyzed to certify the penetration power of FF added by surface coating methodology. Besides, the unique homogeneity index was calculated in order to evaluate the distributional homogeneity of each component. The results demonstrated the reliability of MCR-ALS in studying the distributional homogeneity of FF. It was demonstrated that FF remains mostly on the surface of the pellets with almost no penetration. The rest of the components of the pellets (oil, protein and carbohydrates) were also analyzed. These three nutrients are distributed on the three layers analyzed with a relatively homogeneous location, being carbohydrates (%H = 51 ± 3) the component with the best homogeneous distribution, unlike protein (%H = 45 ± 5), and oil (%H = 40 ± 7). This is the first publication where the penetration of an antibiotic, added with surface-coating to feed pellets, was analyzed with FTIR-ATR imaging and multivariate analysis, showing the contribution these analytical tools can make to the medicated feed industry.

Effects on Lignin Redistribution in Eucalyptus globulus Fibres Pre-Treated by Steam Explosion: A Microscale Study to Cellulose Accessibility.

The objective of this study was to investigate structural changes and lignin redistribution in Eucalyptus globulus pre-treated by steam explosion under different degrees of severity (S0), in order to evaluate their effect on cellulose accessibility by enzymatic hydrolysis. Approximately 87.7% to 98.5% of original glucans were retained in the pre-treated material. Glucose yields after the enzymatic hydrolysis of pre-treated material improved from 19.4% to 85.1% when S0 was increased from 8.53 to 10.42. One of the main reasons for the increase in glucose yield was the redistribution of lignin as micro-particles were deposited on the surface and interior of the fibre cell wall. This information was confirmed by laser scanning confocal fluorescence and FT-IR imaging; these microscopic techniques show changes in the physical and chemical characteristics of pre-treated fibres. In addition, the results allowed the construction of an explanatory model for microscale understanding of the enzymatic accessibility mechanism in the pre-treated lignocellulose.

Erratum: Toro, C. et al. On the Detection of Spectral Emissions of Iron Oxides in Combustion Experiments of Pyrite Concentrates. Sensors 2020, 20, 1284.

The authors wish to make the following corrections to this paper [...].

On the Detection of Spectral Emissions of Iron Oxides in Combustion Experiments of Pyrite Concentrates.

In this paper, we report on the spectral detection of wustite, Fe(II) oxide (FeO), and magnetite, Fe(II, III) oxide (Fe3O4), molecular emissions during the combustion of pyrite (FeS2), in a laboratory-scale furnace operating at high temperatures. These species are typically generated by reactions occurring during the combustion (oxidation) of this iron sulfide mineral. Two detection schemes are addressed: the first consisting of measurements with a built-in developed spectrometer with a high sensitivity and a high spectral resolution. The second one consisting of spectra measured with a low spectral resolution and a low sensitivity commercial spectrometer, but enhanced and analyzed with post signal processing and multivariate data analysis such as principal component analysis (PCA) and a multivariate curve resolution - the alternating least squares method (MCR-ALS). A non-linear model is also proposed to reconstruct spectral signals measured during pyrite combustion. Different combustion conditions were studied to evaluate the capacity of the detection schemes to follow the spectral emissions of iron oxides. The results show a direct correlation between FeO and Fe3O4 spectral features intensity, and non-linear relations with key combustion variables such as flame temperature, and the combusted sulfide mineral particle size.

Fourier-transform infrared imaging and multivariate analysis for direct identification of principal polysaccharides in brown seaweeds.

The current hydrocolloid industry requires new techniques for biomass characterization, which can quickly and ecologically characterize contained sugars. This work proposes the use of Fourier Transform Infrared microspectroscopy in combination with multivariate methods, to localize and identify the main carbohydrates and other components present in fresh brown seaweeds, avoiding time-consuming samples pre-treatments. Infrared images of Macrocystis pyrifera samples were analyzed by Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) and Principal Component Analysis (PCA) as chemometrics techniques to identify the compounds. MCR-ALS was the best strategy, delivering pure spectra of chemical compound that PCA did not. The carbohydrates identified by this method were 1-3-ß-glucans divided into endofibers and laminarin; two types of fucoidans (rich in fucose or mannuronic acid), alginate and mannitol, besides other compounds such as proteins. This technique represents an opportunity for the hydrocolloid industry for a modern, rapid and environmentally-friendly characterization of macroalgal biomass to enhance its use.

Development of Graphene Oxide Composite Aerogel with Proanthocyanidins with Hemostatic Properties As a Delivery System.

The graphene aerogels' potential for use as both a hemostatic agent and dermal delivery system has scarcely been investigated. In this study, we used a sol-gel process for generating dry and stable composite aerogels based on graphene oxide (GO) and poly(vinyl alcohol) (PVA). Furthermore, we incorporated natural extract of País grape seed (SD) and skin (SK), rich in proanthocyanidins (PAs or condensed tannins). The effect of the incorporation of the grape extracts was investigated in relation to the aerogels' structure, coagulation performance and the release of the extracts. The results demonstrated that they have a porous structure and low density, capable of absorbing water and blood. The incorporation of 12% (w/w) of PA extracts into the aerogel increased the negative zeta potential of the material by 33% (-18.3 ± 1.3 mV), and the coagulation time was reduced by 37% and 28% during the first 30 and 60 s of contact between the aerogel and whole blood, respectively. The release of extracts from the GO-PVA-SD and GO-PVA-SK aerogels was prolonged to 3 h with 20%, probably due to the existence of strong binding between PAs andGO-PVA, both characterized by the presence of aromatic and hydroxyl groups that can form noncovalent bonds but are strong and stable enough to avoid a greater release into the medium. This study provides a new GO-based aerogel, which has a great potential use in the field of dermal delivery, wound healing and/or the treatment of trauma bleeding.

Evaluation of the microscopic distribution of florfenicol in feed pellets for salmon by Fourier Transform infrared imaging and multivariate analysis.

Fourier Transform infrared imaging and multivariate analysis were used to identify, at the microscopic level, the presence of florfenicol (FF), a heavily-used antibiotic in the salmon industry, supplied to fishes in feed pellets for the treatment of salmonid rickettsial septicemia (SRS). The FF distribution was evaluated using Principal Component Analysis (PCA) and Augmented Multivariate Curve Resolution with Alternating Least Squares (augmented MCR-ALS) on the spectra obtained from images with pixel sizes of 6.25 µm × 6.25 µm and 1.56 µm × 1.56 µm, in different zones of feed pellets. Since the concentration of the drug was 3.44 mg FF/g pellet, this is the first report showing the powerful ability of the used of spectroscopic techniques and multivariate analysis, especially the augmented MCR-ALS, to describe the FF distribution in both the surface and inner parts of feed pellets at low concentration, in a complex matrix and at the microscopic level. The results allow monitoring the incorporation of the drug into the feed pellets.

Chemical Characterization and Determination of the Anti-Oxidant Capacity of Two Brown Algae with Respect to Sampling Season and Morphological Structures Using Infrared Spectroscopy and Multivariate Analyses.

Brown algae biomass has been shown to be a highly important industrial source for the production of alginates and different nutraceutical products. The characterization of this biomass is necessary in order to allocate its use to specific applications according to the chemical and biological characteristics of this highly variable resource. The methods commonly used for algae characterization require a long time for the analysis and rigorous pretreatments of samples. In this work, nondestructive and fast analyses of different morphological structures from Lessonia spicata and Macrocystis pyrifera, which were collected during different seasons, were performed using Fourier transform infrared (FT-IR) techniques in combination with chemometric methods. Mid-infrared (IR) and near-infrared (NIR) spectral ranges were tested to evaluate the spectral differences between the species, seasons, and morphological structures of algae using a principal component analysis (PCA). Quantitative analyses of the polyphenol and alginate contents and the anti-oxidant capacity of the samples were performed using partial least squares (PLS) with both spectral ranges in order to build a predictive model for the rapid quantification of these parameters with industrial purposes. The PCA mainly showed differences in the samples based on seasonal sampling, where changes were observed in the bands corresponding to polysaccharides, proteins, and lipids. The obtained PLS models had high correlation coefficients (r) for the polyphenol content and anti-oxidant capacity (r > 0.9) and lower values for the alginate determination (0.7 < r < 0.8). Fourier transform infrared-based techniques were suitable tools for the rapid characterization of algae biomass, in which high variability in the samples was incorporated for the qualitative and quantitative analyses, and have the potential to be used on an industrial scale.

Réplica a "Meningitis, punción lumbar y procalcitonina" / Reply to "Meningitis, lumbar puncture and procalcitonin"

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Fourier transform infrared imaging and microscopy studies of Pinus radiata pulps regarding the simultaneous saccharification and fermentation process.

The distribution and chemical patterns of lignocellulosic components at microscopic scale and their effect on the simultaneous saccharification and fermentation process (SSF) in the production of bioethanol from Pinus radiata pulps were analyzed by the application of diverse microscopical techniques, including scanning electronic microscopy (SEM), confocal laser scanning microscopy (CLSM) and attenuated total reflectance (ATR) - Fourier transform infrared microspectroscopy. This last technique was accompanied with multivariate methods, including principal component analysis (PCA) and multivariate curve resolution with alternating least squares (MCR-ALS) to evaluate the distribution patterns and to generate pure spectra of the lignocellulosic components of fibers. The results indicate that the information obtained by the techniques is complementary (ultrastructure, confocality and chemical characterization) and that the distribution of components affects the SSF yield, identifying lignin coalescence droplets as a characteristic factor to increase the SSF yield. Therefore, multivariate analysis of the infrared spectra enabled the in situ identification of the cellulose, lignin and lignin-carbohydrates arrangements. These techniques could be used to investigate the lignocellulosic components distribution and consequently their recalcitrance in many applications where minimal sample manipulation and microscale chemical information is required.

Valoración de la analgesia y efectos colaterales con morfina vs. petidina por vía epidural en pacientes intervenidos de cirugía torácica y urológica. Hospital Nacional Arzobispo Loayza, abrilûjulio 2011 / Assessment of analgesia and side effects with epidural morphine vs. pethidine in patients undergoing thoracic and urological surgery. Hospital Nacional Arzobispo Loayza, April-July 2011

Objetivo: Evaluar y comparar la calidad de la terapia analgésica y la incidencia de efectos colaterales relacionados con el uso de morfina y petidina por vía epidural, en pacientes intervenidos de cirugía torácica y urológica. Material y métodos: Estudio observacional, prospectivo, longitudinal, analítico y simple ciego. La muestra estuvo conformada por dos grupos, de 17 pacientes cada uno, programados para cirugía torácica y urológica en el Hospital Nacional Arzobispo Loayza, entre abril y julio del 2011. El grupo M recibió morfina 70 ug/kg (40 a 100 ug/kg) y el grupo P petidina 1.5 mg/kg (1 a 2 mg/kg) por vía epidural 20 minutos antes del término de la cirugía. El dolor fue evaluado durante veinticuatro horas. Los datos cuantitativos se expresaron en media y los datos cualitativos en porcentajes. Para la evaluación de las variables cuantitativas de distribución no normal se usó la prueba no paramétrica U de Mann-Whitney, para las variables cualitativas se usó la prueba X2 de Pearson y para las variables ordinales se usó ANOVA en medidas repetidas. Resultados: Los grupos fueron comparables en edad, sexo y estado físico de la ASA. La duración de la analgesia para el grupo P fue 14.7 horas y para el grupo M 14.4 horas (p = 0.9). El requerimiento de analgesia de rescate en el grupo M fue de 6 pacientes frente a 2 del grupo P (p = 0.23). Para la valoración del dolor con la escala verbal global y la escala de Andersen, las medidas variaron en el transcurso del tiempo dentro de cada grupo (p < 0.01) y se encontraron diferencias en la comparación entre los pares de grupo por cada momento a favor del grupo M (p < 0.01). Los efectos colaterales fueron menores en el grupo M. Conclusiones: La morfina administrada por vía epidural brinda mejor calidad de analgesia postoperatoria que petidina administrada por la misma vía, presentando menores efectos colaterales.

Objective: To evaluate and compare the quality of analgesic therapy and the incidence of side effects related to the use of epidural morphine and pethidine in patients undergoing thoracic and urological surgery. Material and methods:Observational, prospective, longitudinal, analytical and single blind study. The sample consisted of two groups of 17 patients each one, scheduled for thoracic and urological surgery at the Hospital Nacional Arzobispo Loayza, between April and July 2011. The group M received morphine 70 ug/kg (40 to 100 ug/kg) and group P pethidine 1.5 mg/kg (1 to 2 mg/kg) epidurally 20 minutes before the end of surgery. Pain was assessed for twenty-four hours. Quantitative data were expressed as mean and qualitative data as percentages. For the evaluation of the quantitative variables not normally distributed the nonparametric U Mann-Whitney test was used, for the qualitative variables the PearsonÆs X2 was used, and for the ordinal variables the ANOVA was used in repeated measures. Results: The groups were comparable in age, sex and ASA physical status. The duration of analgesia for group P was 14.7 hours and 14.4 hours for group M (p = 0.9). The requirement for rescue analgesia in group M was 6 patients versus 2 in group P (p = 0.23). For the evaluation of pain, the global verbal scale and the Andersen scale were used, the measures varied over the time within each group (p < 0.01) and differences in favor of the M group were found when the pairs were compared (p < 0.01). Side effects were lower in group M. Conclusions: Epidural morphine provides better postoperative quality of analgesia than pethidine administered by the same route, presenting fewer side effects.

Infrared spectroscopy as alternative to wet chemical analysis to characterize Eucalyptus globulus pulps and predict their ethanol yield for a simultaneous saccharification and fermentation process.

Bioethanol can be obtained from wood by simultaneous enzymatic saccharification and fermentation step (SSF). However, for enzymatic process to be effective, a pretreatment is needed to break the wood structure and to remove lignin to expose the carbohydrates components. Evaluation of these processes requires characterization of the materials generated in the different stages. The traditional analytical methods of wood, pretreated materials (pulps), monosaccharides in the hydrolyzated pulps, and ethanol involve laborious and destructive methodologies. This, together with the high cost of enzymes and the possibility to obtain low ethanol yields from some pulps, makes it suitable to have rapid, nondestructive, less expensive, and quantitative methods to monitoring the processes to obtain ethanol from wood. In this work, infrared spectroscopy (IR) accompanied with multivariate analysis is used to characterize chemically organosolv pretreated Eucalyptus globulus pulps (glucans, lignin, and hemicellulosic sugars), as well as to predict the ethanol yield after a SSF process. Mid (4,000-400 cm(-1)) and near-infrared (12,500-4,000 cm(-1)) spectra of pulps were used in order to obtain calibration models through of partial least squares regression (PLS). The obtained multivariate models were validated by cross validation and by external validation. Mid-infrared (mid-IR)/NIR PLS models to quantify ethanol concentration were also compared with a mathematical approach to predict ethanol yield estimated from the chemical composition of the pulps determined by wet chemical methods (discrete chemical data). Results show the high ability of the infrared spectra in both regions, mid-IR and NIR, to calibrate and predict the ethanol yield and the chemical components of pulps, with low values of standard calibration and validation errors (root mean square error of calibration, root mean square error of validation (RMSEV), and root mean square error of prediction), high correlation between predicted and measured by the reference methods values (R (2) between 0.789 and 0.997), and adequate values of the ratio between the standard deviation of the reference methods and the standard errors of infrared PLS models relative performance determinant (RPD) (greater than 3 for majority of the models). Use of IR for ethanol quantification showed similar and even better results to the obtained with the discrete chemical data, especially in the case of mid-IR models, where ethanol concentration can be estimated with a RMSEV equal to 1.9 g L(-1). These results could facilitate the analysis of high number of samples required in the evaluation and optimization of the processes.

Kinase-mediated trapping of bi-functional conjugates of paclitaxel or vinblastine with thymidine in cancer cells.

In the present work, we explore the possibility of introducing selectivity to existing chemotherapeutics via the design of non-pro-drug, bi-functional molecules comprising a microtubule-binding agent and a substrate for a disease-associated kinase. The design, synthesis, and in vitro biological evaluation of paclitaxel-thymidine and vinblastine-thymidine bi-functional conjugates are reported here. This work provides the first account of 'kinase-mediated trapping' of cancer therapeutics.

The design, synthesis, and evaluation of two universal doxorubicin-linkers: preparation of conjugates that retain topoisomerase II activity.

The design, synthesis, and evaluation of two N-alkylmaleimide aldehydes have been achieved, which upon reductive alkylation with the C3'-amino group of doxorubicin (DOX) permits the preparation of DOX conjugates via Michael addition of thiol-containing vectors. This method enables the mild, facile, and high-throughput preparation of DOX conjugates that retain the basic C3'-nitrogen, a pre-requisite for topoisomerase II inhibition. Seven DOX-amino acid conjugates were prepared, each displaying similar inhibitory activity as the parent drug.

A facile route to paclitaxel C-10 carbamates.

A general protocol for the synthesis of paclitaxel C-10 carbamates is described. The method entails MeI-mediated activation of 2'-O-TBS-7-O-TES-10-O-deacetyl-paclitaxel-10-O-carbonylimidazole prior to reaction with amines. This method is effective for the synthesis of paclitaxel C-10 derivatives, including bifunctional molecules.

Mechanism of action of NB2001 and NB2030, novel antibacterial agents activated by beta-lactamases.

Two potent antibacterial agents designed to undergo enzyme-catalyzed therapeutic activation were evaluated for their mechanisms of action. The compounds, NB2001 and NB2030, contain a cephalosporin with a thienyl (NB2001) or a tetrazole (NB2030) ring at the C-7 position and are linked to the antibacterial triclosan at the C-3 position. The compounds exploit beta-lactamases to release triclosan through hydrolysis of the beta-lactam ring. Like cephalothin, NB2001 and NB2030 were hydrolyzed by class A beta-lactamases (Escherichia coli TEM-1 and, to a lesser degree, Staphylococcus aureus PC1) and class C beta-lactamases (Enterobacter cloacae P99 and E. coli AmpC) with comparable catalytic efficiencies (k(cat)/K(m)). They also bound to the penicillin-binding proteins of S. aureus and E. coli, but with reduced affinities relative to that of cephalothin. Accordingly, they produced a cell morphology in E. coli consistent with the toxophore rather than the beta-lactam being responsible for antibacterial activity. In biochemical assays, they inhibited the triclosan target enoyl reductase (FabI), with 50% inhibitory concentrations being markedly reduced relative to that of free triclosan. The transport of NB2001, NB2030, and triclosan was rapid, with significant accumulation of triclosan in both S. aureus and E. coli. Taken together, the results suggest that NB2001 and NB2030 act primarily as triclosan prodrugs in S. aureus and E. coli.