Portable near-infrared and Raman spectroscopic devices as complementary tools for instantaneous quality control of turmeric powder.

INTRODUCTION: Process analytical technology (PAT) guidance is implemented in the quality assurance of phytocompounds to achieve the Industry 4.0 concept. Near-infrared (NIR) and Raman spectroscopies are feasible for rapid, reliable quantitative analysis through transparent packaging without removing the samples from their original containers. These instruments can serve PAT guidance. OBJECTIVE: This study aimed to develop online portable NIR and Raman spectroscopic methods for quantifying total curcuminoids in turmeric samples through a plastic bag. The method mimicked an in-line measurement mode in PAT compared with placing samples into a glass vessel (at-line mode). MATERIALS AND METHODS: Sixty-three curcuminoid standard-spiked samples were prepared. Then, 15 samples were randomly selected as fixed validation samples, and 40 of the 48 remaining samples were chosen as calibration set. The results obtained from the partial least square regression (PLSR) models constructed by using the spectra acquired from NIR and Raman were compared with the reference values from high-performance liquid chromatography (HPLC). RESULTS: The optimum PLSR model of at-line Raman was achieved with three latent variables and a root mean square error of prediction (RMSEP) of 0.46. Meanwhile, the PLSR model of at-line NIR with one latent variable offered an RMSEP of 0.43. For the in-line mode, PLSR models created from Raman and NIR spectra had one latent variable with RMSEP of 0.49 and 0.42, respectively. The R2 values for prediction were 0.88-0.92. CONCLUSION: The models established from the spectra from portable NIR and Raman spectroscopic devices with the appropriate spectral pretreatments allowed the determination of total curcuminoid contents through plastic bag.

The Evolution of the Intrinsic Flexural Strength of Jute Strands after a Progressive Delignification Process and Their Contribution to the Flexural Strength of PLA-Based Biocomposites.

Biocomposites from poly-(lactic acid) (PLA) and jute strands were prepared, and their flexural strength was analyzed. Jute strands were submitted to a progressive delignification process and the resulting morphology, composition, and crystallinity index were evaluated. Then, PLA biocomposites comprising 30 wt% of jute strands were produced and characterized under flexural conditions. The delignification processes decreased the lignin content and progressively increased the cellulose content. All this resulted in an enhancement of the composite flexural strength. A modified rule of mixtures, and the relation between tensile and flexural properties were used to determine the intrinsic flexural strength (of the jute strands) and their correlation with their physic-chemical characteristics. Equations correlating the intrinsic flexural strength with the crystallinity index, the cellulose content, and the microfibril angle were proposed. These equations show the impact of these properties over the intrinsic properties of the fibers and can help researchers to select appropriate fibers to obtain accurate properties for the composites. Jute strands show their value as reinforcement by increasing the flexural strength of the matrix by 70% and being less expensive and more environmentally friendly than mineral reinforcements. Together with the profitability and the environmental advantages, the mechanical results suggest that these PLA biocomposites are suitable for specific products of different market sectors.

Effective Tensile Strength Estimation of Natural Fibers through Micromechanical Models: The Case of Henequen Fiber Reinforced-PP Composites.

The performance of henequen fibers and polypropylene composites obtained by injection molding with and without coupling agent was evaluated. Henequen fibers are natural non-wood fibers mainly used in textile sector or in thermosetting matrix composites. In this work, henequen fibers have been used as a possible substitute reinforcement material for sized glass fibers. The surface charge density of the materials used was evaluated, as well as the morphology of the fibers inside the material. A significant reduction in the length of the fibers was observed as a consequence of the processing. The use of a 4% coupling agent based on fiber content was found to be effective in achieving significant improvements in the tensile strength of the composites in the reinforcement range studied. The influence of the aspect ratio on the coupling factor was determined, as well as the evaluation of the interface quality. The results obtained demonstrate the great potential of henequen fibers as reinforcement of composite materials, giving rise to strong interfaces with coupling. Finally, the comparison of henequen fiber composites with sized glass fiber composites showed that it is possible to substitute polypropylene composites with 20 wt.% glass fiber for 50 wt.% henequen fibers.

A Comparative Study of Benchtop and Portable NIR and Raman Spectroscopic Methods for the Quantitative Determination of Curcuminoids in Turmeric Powder.

Turmeric consumption is continually increasing worldwide. Curcuminoids are major active constituents in turmeric and are associated with numerous health benefits. A combination of spectroscopic methods and chemometrics shows the suitability of turmeric for food quality control due to advantages such as speed, versatility, portability, and no need for sample preparation. Five calibration models to quantify curcuminoids in turmeric were proposed using benchtop and portable devices. The most remarkable results showed that Raman and NIR calibration models present an excellent performance reporting RMSEP of 0.44% w/w and 0.41% w/w, respectively. In addition, the five proposed methods (FT-IR, Raman, and NIR) were compared in terms of precision and accuracy. The results showed that benchtop and portable methods were in good agreement and that there are no significant differences between them. This study aims to foster the use of portable devices for food quality control in situ by demonstrating their suitability for the purpose.

Nanocomposites Materials of PLA Reinforced with Nanoclays Using a Masterbatch Technology: A Study of the Mechanical Performance and Its Sustainability.

Packaging consumes around 40% of the total plastic production. One of the most important fields with high requirements is food packaging. Food packaging products have been commonly produced with petrol polymers, but due to environmental concerns, the market is being moved to biopolymers. Poly (lactic acid) (PLA) is the most promising biopolymer, as it is bio-based and biodegradable, and it is well established in the market. Nonetheless, its barrier properties need to be enhanced to be competitive with other polymers such as polyethylene terephthalate (PET). Nanoclays improve the barrier properties of polymeric materials if correct dispersion and exfoliation are obtained. Thus, it marks a milestone to obtain an appropriate dispersion. A predispersed methodology is proposed as a compounding process to improve the dispersion of these composites instead of common melt procedures. Afterwards, the effect of the polarity of the matrix was analyzing using polar and surface modified nanoclays with contents ranging from 2 to 8% w/w. The results showed the suitability of the predispersed and concentrated compound, technically named masterbatch, to obtain intercalated structures and the higher dispersion of polar nanoclays. Finally, the mechanical performance and sustainability of the prepared materials were simulated in a food tray, showing the best assessment of these materials and their lower fingerprint.

Research on the Strengthening Advantages on Using Cellulose Nanofibers as Polyvinyl Alcohol Reinforcement.

The present work aims to combine the unique properties of cellulose nanofibers (CNF) with polyvinyl alcohol (PVA) to obtain high-performance nanocomposites. CNF were obtained by means of TEMPO-mediated ((2,2,6,6-Tetramethylpiperidin-1-yl)oxyl) oxidation, incorporated into the PVA matrix by means of compounding in a single-screw co-rotating internal mixer and then processed by means of injection molding. It was found that CNF were able to improve the tensile strength of PVA in 85% when 4.50 wt % of CNF were added. In addition, the incorporation of a 2.25 wt % of CNF enhanced the tensile strength to the same level that when 40 wt % of microsized fibers (stone groundwood pulp, SGW) were incorporated, which indicated that CNF possessed significantly higher intrinsic mechanical properties than microsized fibers. SGW was selected as reference for microsized fibers due to their extended use in wood plastic composites. Finally, a micromechanical analysis was performed, obtaining coupling factors near to 0.2, indicating good interphase between CNF and PVA. Overall, it was found that the use of CNF is clearly advantageous to the use of common cellulosic fibers if superior mechanical properties are desired, but there are still some limitations that are related to processing that restrict the reinforcement content at low contents.

Combined effect of sodium carboxymethyl cellulose, cellulose nanofibers and drainage aids in recycled paper production process.

The present work shows the suitability of using recovered cardboard boxes for the development of high-performance papers through the use of cellulose nanofibers (CNF) and sodium carboxymethyl cellulose (CMC-Na). CNF were prepared by enzymatic hydrolysis using bleached kraft hardwood pulp, while a commercial grade of CMC-Na was used. Both were added in bulk together with polyethylenimine (PEI) as wet-end additive to improve pulp drainability. The combination of 3 wt% CNF and 7.5 wt% CMC-Na double the breaking length of paper. In addition, the use of 0.4 wt% of PEI significantly decreased the Schopper - Riegler degree, while mechanical properties remained almost at the same level. It was found that it is possible to recover and even increase the properties of recycled papers, with the added advantage that no structural damages were caused on the fibres, increasing the life span and recyclability of paper products.

Calibration sets selection strategy for the construction of robust PLS models for prediction of biodiesel/diesel blends physico-chemical properties using NIR spectroscopy.

Even when the feasibility of using near infrared (NIR) spectroscopy combined with partial least squares (PLS) regression for prediction of physico-chemical properties of biodiesel/diesel blends has been widely demonstrated, inclusion in the calibration sets of the whole variability of diesel samples from diverse production origins still remains as an important challenge when constructing the models. This work presents a useful strategy for the systematic selection of calibration sets of samples of biodiesel/diesel blends from diverse origins, based on a binary code, principal components analysis (PCA) and the Kennard-Stones algorithm. Results show that using this methodology the models can keep their robustness over time. PLS calculations have been done using a specialized chemometric software as well as the software of the NIR instrument installed in plant, and both produced RMSEP under reproducibility values of the reference methods. The models have been proved for on-line simultaneous determination of seven properties: density, cetane index, fatty acid methyl esters (FAME) content, cloud point, boiling point at 95% of recovery, flash point and sulphur.

Near infrared spectroscopy combined with multivariate analysis for monitoring the ethanol precipitation process of fraction I+II+III supernatant in human albumin separation.

Nowadays, as a powerful process analytical tool, near infrared spectroscopy (NIRS) has been widely applied in process monitoring. In present work, NIRS combined with multivariate analysis was used to monitor the ethanol precipitation process of fraction I+II+III (FI+II+III) supernatant in human albumin (HA) separation to achieve qualitative and quantitative monitoring at the same time and assure the product's quality. First, a qualitative model was established by using principal component analysis (PCA) with 6 of 8 normal batches samples, and evaluated by the remaining 2 normal batches and 3 abnormal batches. The results showed that the first principal component (PC1) score chart could be successfully used for fault detection and diagnosis. Then, two quantitative models were built with 6 of 8 normal batches to determine the content of the total protein (TP) and HA separately by using partial least squares regression (PLS-R) strategy, and the models were validated by 2 remaining normal batches. The determination coefficient of validation (Rp2), root mean square error of cross validation (RMSECV), root mean square error of prediction (RMSEP) and ratio of performance deviation (RPD) were 0.975, 0.501g/L, 0.465g/L and 5.57 for TP, and 0.969, 0.530g/L, 0.341g/L and 5.47 for HA, respectively. The results showed that the established models could give a rapid and accurate measurement of the content of TP and HA. The results of this study indicated that NIRS is an effective tool and could be successfully used for qualitative and quantitative monitoring the ethanol precipitation process of FI+II+III supernatant simultaneously. This research has significant reference value for assuring the quality and improving the recovery ratio of HA in industrialization scale by using NIRS.

Analysis of ecstasy in oral fluid by ion mobility spectrometry and infrared spectroscopy after liquid-liquid extraction.

We developed and evaluated two different strategies for determining abuse drugs based on (i) the analysis of saliva by ion mobility spectrometry (IMS) after thermal desorption and (ii) the joint use of IMS and infrared (IR) spectroscopy after liquid-liquid microextraction (LLME) to enable the sensitivity-enhanced detection and double confirmation of ecstasy (MDMA) abuse. Both strategies proved effective for the intended purpose. Analysing saliva by IMS after thermal desorption, which provides a limit of detection (LOD) of 160µgL(-1), requires adding 0.2M acetic acid to the sample and using the truncated negative second derivative of the ion mobility spectrum. The joint use of IMS and IR spectroscopy after LLME provides an LOD of 11µgL(-1) with the former technique and 800µgL(-1) with the latter, in addition to a limit of confirmation (LOC) of 1.5mgL(-1). Using IMS after thermal desorption simplifies the operational procedure, and using it jointly with IR spectroscopy after LLME allows double confirmation of MDMA abuse with two techniques based on different principles (viz., IMS drift times and IR spectra). Also, it affords on-site analyses, albeit at a lower throughput.

Detection and characterization of emerging psychoactive substances by ion mobility spectrometry.

Rapid detection and identification of novel psychoactive substances (NPS) continues to present significant analytical challenges to forensic and analytical chemists. Ion mobility spectrometry (IMS) has been traditionally considered as the analytical technique of choice to detect illicit drugs in security points in airports, borderlines and customs. Databases of the reduced mobility (K0 ) values of illicit drugs are available in the scientific literature and they should be completed with data of emerging designer drugs. In this paper, we have evaluated the effect of different measurement conditions and determined the K0 values of an important number of NPS including different families; such as phenethylamines, cathinones, synthetic cannabinoids and tryptamines among others to be incorporated to the existing data to provide a rapid detection and identification of this emerging threat.

Ion mobility spectrometry evaluation of cocaine occupational exposure in forensic laboratories.

An approach, based on ion mobility spectrometry (IMS) has been developed for the control of cocaine in air of the breathing zone of operators, in laboratory surfaces and in nasal mucus of employees to evaluate cocaine exposure in a forensic laboratory. The analytical methodology has been validated in terms of accuracy, precision and limits of detection and results obtained were statistically comparable with those obtained by liquid chromatography. Cocaine concentration in laboratory air increases from 100 ± 35 ng m(-3) of a normal day to 10,000 ng m(-3) during the manipulation of cocaine seizures. The occupational exposure limit (OEL) for cocaine has not been established which difficult the evaluation of the health effects of continuous exposition to very small doses of cocaine. Cocaine was also found in almost all the analyzed sample surfaces and also was found in nasal mucus of the police officers that were present during the manipulation of cocaine seizures without using a face mask. In summary, cocaine concentrations could present a health hazard to the employees and therefore warrants remediation and some modifications of the manipulation operations have been proposed.

Near-infrared imaging for high-throughput screening of moisture induced changes in freeze-dried formulations.

Evaluation of freeze-dried biopharmaceutical formulations requires careful analysis of multiple quality attributes. The aim of this study was to evaluate the use of near-infrared (NIR) imaging for fast analysis of water content and related physical properties in freeze-dried formulations. Model formulations were freeze-dried in well plates. Samples were imaged with a NIR hyperspectral camera after freeze-drying and upon storage. On the basis of Karl Fischer titration reference values, a univariate quantification model was constructed and used to visualize the distribution of water within freeze-dried samples. Differences observed between samples stored at 11% and 43% relative humidity (RH) were found to be related to the amount of amorphous component in the sample. When stored at 43% RH, the moisture content in samples with high sucrose content increased within 2 days and some degree of localized drying was observed within the samples after 3 days of storage. Further investigations with X-ray powder diffraction confirmed this local drying to be related to crystallization of sucrose. The combination of fast analysis of water content and spatial solid-state information makes NIR imaging a powerful tool for formulation development of freeze-dried samples.

Noninvasive double confirmation of cocaine abuse.

A double confirmation procedure, based on the combined application of Ion Mobility Spectrometry (IMS) and Infrared Spectroscopy (IR), has been developed for the noninvasive unambiguous identification of cocaine consume. The use of nasal mucus as a biological specimen for cocaine abuse confirmation has been proposed as an alternative to the use of blood and urine due to its noninvasive character and the presence of the parent compound instead of its metabolites. Sampling conditions, interferences caused by cutting agents and other substances, and limits of identification (LOI) and confirmation (LOC) have been deeply evaluated. The procedure combines the high sensitivity of the IMS to identify positive samples with the high selectivity of the IR procedure to confirm positive results. Thus, the proposed two tier method has been applied to the detection and identification of cocaine in the nasal mucus of different individuals, consumers, and nonconsumers, providing results comparable with those obtained by a reference procedure.

Real-time determination of critical quality attributes using near-infrared spectroscopy: a contribution for Process Analytical Technology (PAT).

Process Analytical Technology (PAT) is playing a central role in current regulations on pharmaceutical production processes. Proper understanding of all operations and variables connecting the raw materials to end products is one of the keys to ensuring quality of the products and continuous improvement in their production. Near infrared spectroscopy (NIRS) has been successfully used to develop faster and non-invasive quantitative methods for real-time predicting critical quality attributes (CQA) of pharmaceutical granulates (API content, pH, moisture, flowability, angle of repose and particle size). NIR spectra have been acquired from the bin blender after granulation process in a non-classified area without the need of sample withdrawal. The methodology used for data acquisition, calibration modelling and method application in this context is relatively inexpensive and can be easily implemented by most pharmaceutical laboratories. For this purpose, Partial Least-Squares (PLS) algorithm was used to calculate multivariate calibration models, that provided acceptable Root Mean Square Error of Predictions (RMSEP) values (RMSEP(API)=1.0 mg/g; RMSEP(pH)=0.1; RMSEP(Moisture)=0.1%; RMSEP(Flowability)=0.6 g/s; RMSEP(Angle of repose)=1.7° and RMSEP(Particle size)=2.5%) that allowed the application for routine analyses of production batches. The proposed method affords quality assessment of end products and the determination of important parameters with a view to understanding production processes used by the pharmaceutical industry. As shown here, the NIRS technique is a highly suitable tool for Process Analytical Technologies.

Determination of drug, excipients and coating distribution in pharmaceutical tablets using NIR-CI.

The growing interest of the pharmaceutical industry in Near Infrared-Chemical Imaging (NIR-CI) is a result of its high usefulness for quality control analyses of drugs throughout their production process (particularly of its non-destructive nature and expeditious data acquisition). In this work, the concentration and distribution of the major and minor components of pharmaceutical tablets are determined and the spatial distribution from the internal and external sides has been obtained. In addition, the same NIR-CI allowed the coating thickness and its surface distribution to be quantified. Images were processed to extract the target data and calibration models constructed using the Partial Least Squares (PLS) algorithms. The concentrations of Active Pharmaceutical Ingredient (API) and excipients obtained for uncoated cores were essentially identical to the nominal values of the pharmaceutical formulation. But the predictive ability of the calibration models applied to the coated tablets decreased as the coating thickness increased.

Determination of trace impurities in cosmetic intermediates by ion mobility spectrometry.

The cosmetic and pharmaceutical industries are continuously demanding fast, efficient, cost-effective analytical methods to monitor production processes and assure end-product quality. The presence of residual reagents or impurities formed during a synthetic process can have an adverse impact on product quality, assurance of which requires using increasingly sensitive analytical methods to facilitate the detection and/or determination of toxic compounds with potentially hazardous effects on consumer's health. In this work, we assessed the potential of ion mobility spectrometry (IMS) for the detection and quantitation of dimethylaminopropylamine (DMAPA) residues in stearamidopropyldimethylamine (SAPDA) production samples. The influence of instrumental variables including solvent, solution drying time, injected volume and volatilization temperature was examined. The ensuing analytical method takes less than 1 min per analysis and uses only a few microlitres of sample. The calibration curve was linear over the DMAPA concentration range 0.030-0.500 µg mL(-1). The proposed method was validated for use in control processes. The complex plasmagram for amidoamines allows the origin of cosmetic oils to be easily, expeditiously identified. Based on the results, IMS holds great promise for the qualitative and quantitative determination of the studied amide and various others in cosmetic products.

A review of recent, unconventional applications of ion mobility spectrometry (IMS).

The applications of ion mobility spectrometry (IMS) have grown exponentially beyond its uses for explosive, illicit drug and chemical warfare agent monitoring in recent years. Instrumental developments including new drift tube materials and ionization sources have enabled the manufacturing of more sophisticated and affordable IMS equipment for the advantageous analysis of samples with no pretreatment. The most recent applications of IMS include quality control and cleaning validation procedures in the pharmaceutical industry; determinations of contaminants in food samples; clinical analyses of biological fluids; environmental analyses of contaminants in gaseous, liquid and solid samples; and (bio)process quality control monitoring. Coupling IMS with MS(n) has enabled the analysis of very complex samples and the extraction of knowledge unavailable from isolated MS measurements, especially in the polymer and petroleomic industries.

Quality by design approach of a pharmaceutical gel manufacturing process, part 1: determination of the design space.

This work was conducted in the framework of a quality by design project involving the production of a pharmaceutical gel. Preliminary work included the identification of the quality target product profiles (QTPPs) from historical values for previously manufactured batches, as well as the critical quality attributes for the process (viscosity and pH), which were used to construct a D-optimal experimental design. The experimental design comprised 13 gel batches, three of which were replicates at the domain center intended to assess the reproducibility of the target process. The viscosity and pH models established exhibited very high linearity and negligible lack of fit (LOF). Thus, R(2) was 0.996 for viscosity and 0.975 for pH, and LOF was 0.53 for the former parameter and 0.84 for the latter. The process proved reproducible at the domain center. Water content and temperature were the most influential factors for viscosity, and water content and acid neutralized fraction were the most influential factors for pH. A desirability function was used to find the best compromise to optimize the QTPPs. The body of information was used to identify and define the design space for the process. A model capable of combining the two response variables into a single one was constructed to facilitate monitoring of the process.

Quality by design approach of a pharmaceutical gel manufacturing process, part 2: near infrared monitoring of composition and physical parameters.

We applied the principles of quality by design to the production process of a pharmaceutical gel by using the near infrared spectroscopy (NIRS) technique in combination with multivariate chemometric tools. For this purpose, we constructed a D-optimal experimental design having normal operational condition (NOC) batches as central point. The primary aim here was to develop an expeditious NIRS method for determining the composition of a pharmaceutical gel and assess the temporal changes in major physical factors affecting the quality of the product (specifically, viscosity and pH). Gel components were quantified by using partial least squares (PLS) calibration models of the PLS1 type. The study was completed by using the batch statistical process control method to compare product batches included in the experimental design with NOC batches. Similarities and differences between the two types of batches were identified by using control charts for residuals (Q-statistic) and Hotteling's T2 (D-statistic). The ensuing models, which were subject to errors less than 5%, allowed the gel production process to be effectively monitored. As shown in this work, the NIRS technique is a highly suitable tool for process analytical technology.