Preparation and Characterization of a Rifampicin Coamorphous Material with Tromethamine Coformer: An Experimental-Theoretical Study.

Rifampicin (RIF) is an antibiotic used to treat tuberculosis and leprosy. Even though RIF is a market-available drug, it has a low aqueous solubility, hindering its bioavailability. Among the strategies for bioavailability improvement of poorly soluble drugs, coamorphous systems have been revealed as an alternative in the increase of the aqueous solubility of drug systems and at the same time also increasing the amorphous state stability and dissolution rate when compared with the neat drug. In this work, a new coamorphous form from RIF and tromethamine (TRIS) was synthesized by slow evaporation. Structural, electronic, and thermodynamic properties and solvation effects, as well as drug-coformer intermolecular interactions, were studied through density functional theory (DFT) calculations. Powder X-ray diffraction (PXRD) data allowed us to verify the formation of a new coamorphous. In addition, the DFT study indicates a possible intermolecular interaction by hydrogen bonds between the available amino and carbonyl groups of RIF and the hydroxyl and amino groups of TRIS. The theoretical spectra obtained are in good agreement with the experimental data, suggesting the main interactions occurring in the formation of the coamorphous system. PXRD was used to study the physical stability of the coamorphous system under accelerated ICH conditions (40 °C and 75% RH), indicating that the material remained in an amorphous state up to 180 days. The thermogravimetry result of this material showed a good thermal stability up to 153 °C, and differential scanning calorimetry showed that the glass temperature (Tg) was at 70.0 °C. Solubility studies demonstrated an increase in the solubility of RIF by 5.5-fold when compared with its crystalline counterpart. Therefore, this new material presents critical parameters that can be considered in the development of new coamorphous formulations.

Therapeutic Liquid Eutectic Solvents in Lipid Nanoparticles as Drug Vehicles-A Proof of Concept.

Tuberculosis is an infectious disease caused by the bacterial complex Mycobacterium tuberculosis. Despite the decline in the incidence and mortality of this disease over the years, the emergence of new strains of tuberculosis resistant to existing tuberculostatic drugs is currently one of the largest public health problems. The engineering and development of new drugs is a complex process; therefore, the modification and enhancement of the drugs already marked is a better and faster solution. Ethambutol (ETB) is an antimycobacterial drug used to treat tuberculosis; however, it is highly hygroscopic and is sparingly soluble in water. Therapeutic Deep Eutectic Solvents (THEDESs) are known to improve drug solubility, permeability, and hygroscopicity, among others. In this study, three THEDESs of ETB were synthesized with sucralose, glucose and glycerol and then encapsulated in nanostructured lipid carriers to improve their stability. This work is a proof of concept on the possibility of encapsulating the THEDESs, and results show that the encapsulation of ETB is possible, yielding formulations with a loading capacity superior to 8.5% and able to incorporate THEDESs and not just ETB.

Subcritical Water Extraction to Valorize Grape Biomass-A Step Closer to Circular Economy.

With the increase in the world population, the overexploitation of the planet's natural resources is becoming a worldwide concern. Changes in the way humankind thinks about production and consumption must be undertaken to protect our planet and our way of living. For this change to occur, sustainable development together with a circular economic approach and responsible consumption are key points. Agriculture activities are responsible for more than 10% of the greenhouse gas emissions; moreover, by 2050, it is expected that food production will increase by 60%. The valorization of food waste is therefore of high importance to decrease the environmental footprint of agricultural activities. Fruits and vegetables are wildly consumed worldwide, and grapes are one of the main producers of greenhouse gases. Grape biomass is rich in bioactive compounds that can be used for the food, pharmaceutical and cosmetic industries, and their extraction from this food residue has been the target of several studies. Among the extraction techniques used for the recovery of bioactive compounds from food waste, subcritical water extraction (SWE) has been the least explored. SWE has several advantages over other extraction techniques such as microwave and ultrasound extraction, allowing high yields with the use of only water as the solvent. Therefore, it can be considered a green extraction method following two of the principles of green chemistry: the use of less hazardous synthesis (principle number 3) and the use of safer solvents and auxiliaries (principle number 5). In addition, two of the green extraction principles for natural products are also followed: the use of alternative solvents or water (principle number 2) and the use of a reduced, robust, controlled and safe unit operation (principle number 5). This review is an overview of the extraction process using the SWE of grape biomass in a perspective of the circular economy through valorization of the bioactive compounds extracted. Future perspectives applied to the SWE are also discussed, as well as its ability to be a green extraction technique.

Mechanochemistry in Portugal-A Step towards Sustainable Chemical Synthesis.

In Portugal, publications with mechanochemical methods date back to 2009, with the report on mechanochemical strategies for the synthesis of metallopharmaceuticals. Since then, mechanochemical applications have grown in Portugal, spanning several fields, mainly crystal engineering and supramolecular chemistry, catalysis, and organic and inorganic chemistry. The area with the most increased development is the synthesis of multicomponent crystal forms, with several groups synthesizing solvates, salts, and cocrystals in which the main objective was to improve physical properties of the active pharmaceutical ingredients. Recently, non-crystalline materials, such as ionic liquids and amorphous solid dispersions, have also been studied using mechanochemical methods. An area that is in expansion is the use of mechanochemical synthesis of bioinspired metal-organic frameworks with an emphasis in antibiotic coordination frameworks. The use of mechanochemistry for catalysis and organic and inorganic synthesis has also grown due to the synthetic advantages, ease of synthesis, scalability, sustainability, and, in the majority of cases, the superior properties of the synthesized materials. It can be easily concluded that mechanochemistry is expanding in Portugal in diverse research areas.

Vibrational Spectroscopy for Cocrystals Screening. A Comparative Study.

A recurrent problem faced by the pharmaceutical industry when formulating drug products concerns poorly soluble drugs, which, despite having desirable pharmacological activity, present limited bioavailability. Cocrystallization is growing up as a possible approach to tackle this problem. Cocrystals are crystalline materials comprising at least two components, solid at room temperature, and held together by non-covalent bonds. The increasing interest in these compounds is steadily demanding faster, simpler, and more reliable methods for the task of screening new cocrystals. This work aims at comparing the performance of three vibrational spectroscopy techniques (mid infrared, near infrared, and Raman spectroscopy) for cocrystals screening. Presented results are based on hydrochlorothiazide, a poorly soluble drug belonging to class IV of the Biopharmaceutical Classification System. The implemented cocrystal screening procedure tested six coformers (all considered safe for human administration) added according to a drug:coformer ratio of 1:1 and 1:2 and seven solvents with different polarity. The screening method chosen was based on slurry cocrystallization performed by sonication (ultrasound assisted) in a 96-well plate. Results show that all evaluated vibrational spectroscopy techniques provided important information regarding cocrystal formation, including information on the groups involved in the cocrystallization and purity, and can be used for the screening task.

A Comprehensive Review on Deep Eutectic Solvents and Its Use to Extract Bioactive Compounds of Pharmaceutical Interest.

The extraction of bioactive compounds of pharmaceutical interest from natural sources has been significantly explored in recent decades. However, the extraction techniques used were not very efficient in terms of time and energy consumption; additionally, the solvents used for the extraction were harmful for the environment. To improve the environmental impact of the extractions and at the same time increase the extraction yields, several new extraction techniques were developed. Among the most used ones are ultrasound-assisted extraction and microwave-assisted extraction. These extraction techniques increased the yield and selectivity of the extraction in a smaller amount of time with a decrease in energy consumption. Nevertheless, a high volume of organic solvents was still used for the extraction, causing a subsequent environmental problem. Neoteric solvents appeared as green alternatives to organic solvents. Among the neoteric solvents, deep eutectic solvents were evidenced to be one of the best alternatives to organic solvents due to their intrinsic characteristics. These solvents are considered green solvents because they are made up of natural compounds such as sugars, amino acids, and carboxylic acids having low toxicity and high degradability. In addition, they are simple to prepare, with an atomic economy of 100%, with attractive physicochemical properties. Furthermore, the huge number of compounds that can be used to synthesize these solvents make them very useful in the extraction of bioactive compounds since they can be tailored to be selective towards a specific component or class of components. The main aim of this paper is to give a comprehensive review which describes the main properties, characteristics, and production methods of deep eutectic solvents as well as its application to extract from natural sources bioactive compounds with pharmaceutical interest. Additionally, an overview of the more recent and sustainable extraction techniques is also given.

A New Microwave-Assisted Protocol for Cellulose Extraction from Eucalyptus and Pine Tree Wood Waste.

An enormous interest in the development of efficient protocols for cellulose extraction has been demonstrated in the last few years, although usually based on non-sustainable chemical and thermal approaches. In this work, we propose a new and more sustainable method for cellulose extraction from eucalyptus and pine tree wood waste products exclusively performed using microwave-assisted radiation. The methodology includes three main steps: (i) alkaline treatment; (ii) bleaching I, using H2O2; and (iii) bleaching II, an acidic treatment. Samples obtained in each step were characterized by Fourier-transform Infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results were compared with the structural and thermal profile of the starting materials, a commercially available microcrystalline cellulose and with an industrial paper pulp sample. Results confirmed that for both types of wood wastes, cellulose was retained during the extraction procedures and that the removal of hemicellulose and lignin was mainly achieved in the last step, as seen by the FTIR spectra and TGA curves. The developed protocol is innovative, as it constitutes an easy and quick approach for extracting cellulose from eucalyptus and pine tree wood waste. Mild chemical and thermal conditions are used during the three extraction steps (microwave irradiation, aqueous solutions, maximum of 120 °C in a total of 3 h). Moreover, environmentally friendly purification steps are applied based on the use of water and ethanol. This approach offers the possibility of a future scale-up study to potentially apply the developed protocol to the extraction of cellulose on an industrial scale.

Solids Turn into Liquids-Liquid Eutectic Systems of Pharmaceutics to Improve Drug Solubility.

The low solubility of active pharmaceutical ingredients (APIs) is a problem in pharmaceutical development. Several methodologies can be used to improve API solubility, including the use of eutectic systems in which one of the constituents is the API. This class of compounds is commonly called Therapeutic Deep Eutectic Systems (THEDES). THEDES has been gaining attention due to their properties such as non-toxicity, biodegradability, and being non-expensive and easy to prepare. Since the knowledge of the solid liquid diagram of the mixture and the ideal eutectic point is necessary to ascertain if a mixture is a deep eutectic or just a eutectic mixture that is liquid at ambient temperature, the systems studied in this work are called Therapeutic Liquid Eutectic Systems (THELES). Therefore, the strategy proposed in this work is to improve the solubility of chlorpropamide and tolbutamide by preparing THELES. Both APIs are sulfonylurea compounds used for the treatment of type 2 diabetes mellitus and have low solubility in water. To prepare the THELES, several coformers were tested, namely, tromethamine, L(+)-arginine, L-tryptophan, citric acid, malic acid, ascorbic acid, and p-aminobenzoic acid, in molar ratios of 1:1 and 1:2. To improve viscosity, water was added in different molar ratios to all systems. THELES were characterized by mid-infrared spectroscopy (MIR), and differential scanning calorimetry. Their viscosity, solubility, and permeability were also determined. Their stability at room temperature and 40 °C was accessed by MIR. Cytocompatibility was performed by metabolic activity and cell lysis evaluation, according to ISO10993-5:2009, and compared with the crystalline APIs. THELES with TRIS were successfully synthesized for both APIs. Results showed an increased solubility without a decrease in the permeability of the APIs in the THELES when compared with the pure APIs. The THELES were also considered stable for 8 weeks at ambient temperature. The cells studied showed that the THELES were not toxic for the cell lines used.

Structural, thermal, vibrational, solubility and DFT studies of a tolbutamide co-amorphous drug delivery system for treatment of diabetes.

Among the strategies for bioavailability improvement of poorly soluble drugs, co-amorphous systems have revealed to have a significant impact in the increase of the aqueous solubility of the drug, and at the same time increasing the amorphous state stability and dissolution rate when compared with the neat drug. Tolbutamide (TBM) is an oral hypoglycemic drug largely used in the treatment of type II Mellitus diabetes. TBM is a class II drug according to the Biopharmaceutical Classification System, meaning that it has low solubility and higher permeability. The aim of this study was to synthesize a co-amorphous material of tolbutamide (TBM) with tromethamine (TRIS). Density functional theory (DFT), allowed to study the structural, electronic, and thermodynamic properties, as well as solvation effects. In same theory level, several interactions tests were performed to obtain the most thermodynamically favorable drug-coformer intermolecular interactions. The vibrational spectra (mid infrared and Raman spectroscopy) are in accordance with the theoretical studies, showing that the main molecular interactions are due to the carbonyl, sulfonyl, and amide groups of TMB and the alcohol and amine groups of TRIS. X-ray powder diffraction was used to study the physical stability in dry condition at 25 °C of the co-amorphous system, indicating that the material remained in an amorphous state up to 90 days. Differential scanning calorimetry and thermogravimetric results showed a high increase of the Tg when compared with the amorphous neat drug, from 4.3 °C to 83.7 °C, which generally translated into good physical stability. Solubility studies demonstrated an increase in the solubility of TBM by 2.5 fold when compared with its crystalline counterpart.

Comparison of different chemometric and analytical methods for the prediction of particle size distribution in pharmaceutical powders.

This work compares the estimation of the particle size distribution of a pharmaceutical powder using near-infrared spectroscopy (NIRS), powder flowability properties, and components concentration. The estimations were made by considering the former data blocks separately and together using a multi-block approach. The powders were based on a formulation of paracetamol as the pharmaceutical active ingredient. The reference method used to determine particle size distribution was sieving. Partial least squares methods were used to estimate the multivariate regression models, and the results were compared in terms of figures of merit. It was shown that the partial least squares methods gave similar prediction errors. Regarding the data blocks used, the NIRS block was proven the most advantageous to estimate the particle size distribution. The prediction error of the NIRS block was similar to the other data blocks with additional advantages such as less generalization problems and the possibility of its use to predict additional physical and chemical properties with an improvement to analysis time. The multi-block approach produced the worst results but nevertheless allowed a deeper understanding of the individual contributions of the data blocks in the prediction of the particle size distribution.

Determination of co-crystal phase purity by mid infrared spectroscopy and multiple curve resolution.

Multivariate Curve Resolution (MCR) was used to determine the phase purity of pharmaceutical co-crystals from mid infrared spectra. An in-silico coformer screening was used to choose one of ten potential coformers. This analysis used quantum chemistry simulation to predict which coformers are thermodynamically inclined to form cocrystals with the model drug, hydrochlorothiazide. The coformer chosen was nicotinamide. An experimental solvent screening by ultrasound assisted slurry co-crystallization was performed to evaluate the capacity of the method to determine phase purity. Afterwards, slurry and slow evaporation co-crystallizations were performed at 10, 25, and 40 °C using 7 solvent systems, and two levels of agitation for the evaporation co-crystallization (on and off). Mid infrared spectroscopy (MIRS) analysis of the products of these co-crystallizations was used to develop an MCR model to determine co-crystal phase purity. The MCR results were compared with a reference co-crystal. Experimental design (DoE) was used to investigate the effect of solvents, temperature, and agitation on the purity of co-crystals produced by slurry and evaporation co-crystallization. DoE revealed that evaporation co-crystallization with agitating at 65 rpm formed co-crystals with greater phase purity. The optimal temperature varied with the solvent used.

How can oral paediatric formulations be improved? A challenge for the XXI century.

Paediatric oral formulations need to be improved. This is an indisputable fact that has gain attention from the regulators, the medical staff, and researchers. The lack of adequate medicines developed for children, resulted in several off-label and unlicensed prescriptions, increasing the risks of adverse drug reactions. When formulating a paediatric medicine, it is necessary to consider the product acceptability determined by the characteristics of both product and user (Gerrard et al., 2019). In the last decades, the regulators have issued guidelines to facilitate the development of medicines specialized for children. The use of oral solid dosage forms instead of liquid dosage forms has been preferred due to advantages, e.g., increase stability and shelf-life. However, palatability and size are common difficulties in solid forms. Many aspects need to be considered when developing a new oral paediatric formulation, although, palatability is recognized as a common reason for non-compliance among children. There are many methods that can be used to improve palatability; however, innovative approaches are still needed. In this review, an overview on oral paediatric formulations with emphasis on their palatability is given. Some of the most innovative approaches are discussed, for example, the use of crystal engineering to improve drug palatability, the development of candy-like pharmaceutical forms, and the use of 3D printing to develop personalized medicines for children.

Considerations on high-throughput cocrystals screening by ultrasound assisted cocrystallization and vibrational spectroscopy.

For industrial production of cocrystals, screening phase is essential, helping to become the process faster, more effective and efficient, reducing the quantity of reactants used and associated costs. High-throughput screening (HTS) methods can analyze a wide range of compounds simultaneously. As an answer to industrial necessity of more efficient screening methods, different methods must be developed and optimized. Vibrational spectroscopic techniques are fast, non-destructive and non-invasive, do not need pre-treatment of the samples and allow obtaining qualitative and quantitative information. They are useful in cocrystal analysis, once they detect weak interaction as hydrogen bonding, the basis of cocrystal formation. Therefore, its application in the analysis of cocrystal screening methods, together with multivariate analysis, should be studied in detail. For this end, a HTS procedure of hydrochlorothiazide (HTZ) cocrystals is performed using a 96-well plate and ultrasound-assisted cocrystallization. Six coformers were tested considering ratios of HTZ:coformer of 1:1 and 1:2. The cocrystallization products were analyzed by mid infrared spectroscopy and Raman microspectroscopy. Nicotinamide and p-aminobenzoic acid formed cocrystals with HTZ. The systems with arginine showed that the coformer suffered amorphization; however, no proof of the solid state of HTZ was obtained. The results were not conclusive for the system with citric acid. Additionally, in the nicotinamide and citric acid systems, the physical mixture of the plate also reacted without the present of solvent. Overall, the use of mid infrared spectroscopy and multivariate data analysis provided important information on cocrystal formation, purity, and correct ratio assessment.

Quantitative monitoring of an activated sludge reactor using on-line UV-visible and near-infrared spectroscopy.

The performance of an activated sludge reactor can be significantly enhanced through use of continuous and real-time process-state monitoring, which avoids the need to sample for off-line analysis and to use chemicals. Despite the complexity associated with wastewater treatment systems, spectroscopic methods coupled with chemometric tools have been shown to be powerful tools for bioprocess monitoring and control. Once implemented and optimized, these methods are fast, nondestructive, user friendly, and most importantly, they can be implemented in situ, permitting rapid inference of the process state at any moment. In this work, UV-visible and NIR spectroscopy were used to monitor an activated sludge reactor using in situ immersion probes connected to the respective analyzers by optical fibers. During the monitoring period, disturbances to the biological system were induced to test the ability of each spectroscopic method to detect the changes in the system. Calibration models based on partial least squares (PLS) regression were developed for three key process parameters, namely chemical oxygen demand (COD), nitrate concentration (N-NO(3)(-)), and total suspended solids (TSS). For NIR, the best results were achieved for TSS, with a relative error of 14.1% and a correlation coefficient of 0.91. The UV-visible technique gave similar results for the three parameters: an error of approximately 25% and correlation coefficients of approximately 0.82 for COD and TSS and 0.87 for N-NO(3)(-) . The results obtained demonstrate that both techniques are suitable for consideration as alternative methods for monitoring and controlling wastewater treatment processes, presenting clear advantages when compared with the reference methods for wastewater treatment process qualification.

Optimization of Experimental Settings for the Assessment of Reactive Oxygen Species Production by Human Blood.

The purpose of an experimental design is to improve the productivity of experimentation. It is an efficient procedure for planning experiments, so the data obtained can be analyzed to yield a valid and objective conclusion. This approach has been used as an important tool in the optimization of different analytical approaches. A D-optimal experimental design was used here, for the first time, to optimize the experimental conditions for the detection of reactive oxygen species (ROS) produced by human blood from healthy donors, a biological matrix that better resembles the physiologic environment, following stimulation by a potent inflammatory mediator, phorbol-12-myristate-13-acetate (PMA). For that purpose, different fluorescent probes were used, as 2',7'-dichlorodihydrofluorescein diacetate (DCFH-DA), 2-[6-(4'-amino)-phenoxy-3H-xanthen-3-on-9-yl] benzoic acid (APF), and 10-acetyl-3,7-dihydroxyphenoxazine (amplex red). The variables tested were the human blood dilution, and the fluorescent probe and PMA concentrations. The experiments were evaluated using the Response Surface Methodology and the method was validated using specific compounds. This model allowed the search for optimal conditions for a set of responses simultaneously, enabling, from a small number of experiments, the evaluation of the interaction between the variables under study. Moreover, a cellular model was implemented and optimized to detect the production of ROS using a yet nonexplored matrix, which is human blood.

In-Depth Evaluation of Data Collected During a Continuous Pharmaceutical Manufacturing Process: A Multivariate Statistical Process Monitoring Approach.

The present work presents an in-depth evaluation of continuously collected data during a twin-screw granulation and drying process performed on a continuous manufacturing line. During operation, the continuous line logs 49 univariate process variables, hence generating a large amount of data. Three identical 5-h continuous manufacturing runs were performed. Multivariate data analysis tools, more specifically latent variable modeling tools such as principal component analysis, were used to extract information from the generated data sets unveiling process trends and drifts. Furthermore, a statistical process monitoring strategy is presented. The approach is based on the application of multivariate statistical process monitoring to model the variables that remain around a steady state.

Pharmaceutical cocrystallization techniques. Advances and challenges.

Cocrystals are homogenous (single-phase) crystalline structures composed by two or more components in a definite stoichiometric ratio bonded together by noncovalent bonds. Pharmaceutical industry has been showing interest in cocrystals due to their ability to improve active pharmaceutical ingredients (API's) properties, such as solubility, dissolution, bioavailability, stability and processability. The necessity for high-throughput screening methods and methods capable of producing cocrystals in an industrial scale still hinders the use of cocrystals by the pharmaceutical industry. The aim of this review is to present an extensive overview of the cocrystallization methods, focusing in the specificities of each technique, its advantages and disadvantages. The review is divided into solvent-based and solvent-free methods. The most appropriate methods to the different stages of cocrystals manufacture, from the screening phase to industrial production are identified. The use of continuous and scalable methods in cocrystal production as well as the implementation of quality-by-design and process analytical technology concepts are also addressed.

Synthesis of a Glibenclamide Cocrystal: Full Spectroscopic and Thermal Characterization.

A cocrystal of glibenclamide, an antidiabetic drug classified as type II compound according to the Biopharmaceutics Classification System, has been synthesized using tromethamine as coformer in 1:1 molar ratio, by slow solvent evaporation cocrystalization. The cocrystal obtained was characterized by X-ray powder diffraction, differential scanning calorimetry, Raman, mid infrared, and near-infrared spectroscopy. The results consistently show the formation of a cocrystal between active pharmaceutical ingredients and conformer with the synthons corresponding to hydrogen bonding between hydrogen in amines of tromethamine and carbonyl and sulfonyl groups in glibenclamide.

Statistical process control of cocrystallization processes: A comparison between OPLS and PLS.

Orthogonal partial least squares regression (OPLS) is being increasingly adopted as an alternative to partial least squares (PLS) regression due to the better generalization that can be achieved. Particularly in multivariate batch statistical process control (BSPC), the use of OPLS for estimating nominal trajectories is advantageous. In OPLS, the nominal process trajectories are expected to be captured in a single predictive principal component while uncorrelated variations are filtered out to orthogonal principal components. In theory, OPLS will yield a better estimation of the Hotelling's T2 statistic and corresponding control limits thus lowering the number of false positives and false negatives when assessing the process disturbances. Although OPLS advantages have been demonstrated in the context of regression, its use on BSPC was seldom reported. This study proposes an OPLS-based approach for BSPC of a cocrystallization process between hydrochlorothiazide and p-aminobenzoic acid monitored on-line with near infrared spectroscopy and compares the fault detection performance with the same approach based on PLS. A series of cocrystallization batches with imposed disturbances were used to test the ability to detect abnormal situations by OPLS and PLS-based BSPC methods. Results demonstrated that OPLS was generally superior in terms of sensibility and specificity in most situations. In some abnormal batches, it was found that the imposed disturbances were only detected with OPLS.

Merging vibrational spectroscopic data for wine classification according to the geographic origin.

The wine making procedure is no longer a secret and it is nowadays well described and repeated around the world. Nevertheless, wines present unique features, strongly associated with their geographic origin. Classification systems were developed to catalogue wines according to the provenance, and are currently established by official authorities in order to ensure wine authenticity. The use of near-infrared (NIR), mid-infrared (MIR) and Raman spectroscopy for tracing the origin of wine samples, has been reported with different levels of success. This work evaluated and compared the performance of these techniques, as well as their joint use, in terms of geographic origin classification. NIR, MIR and Raman spectra of wine samples belonging to four Portuguese wine regions (Vinhos Verdes, Lisboa, Açores and Távora-Varosa) were analyzed by partial least squares discriminant analysis (PLS-DA). Results revealed the better suitability of MIR spectroscopy (87.7% of correct predictions) over NIR (60.4%) and Raman (60.8%). The joint use of spectral sets did not improve the predictive ability of the models. The best models were achieved by combining MIR and NIR spectra resulting in 86.7% of correct predictions. Multiblock partial least squares (MB-PLS) models were developed to further explore the combination of spectral data. Although these models did not improve the percentage of correct predictions, they demonstrated the higher contribution of MIR spectroscopic data, in the development of the models.