Methods In Pharmaceutical Analysis Research Articles

Application of signal processing techniques for the spectroscopic analysis of dolutegravir and lamivudine: a comparative assessment and greenness appraisal

HIV treatment has greatly improved over the years, with the introduction of antiretroviral drugs that target the virus and suppress its replication. Dolutegravir and lamivudine are two such antiretroviral drugs that are commonly used in HIV treatment regimens. Herein, three spectrophotometric methods manipulating ratio spectra were developed for the simultaneous analysis of dolutegravir and lamivudine in their binary mixtures. These methods include mathematical processing stages like ratio difference method or signal processing approaches such as the first derivative of the ratio spectra, and continuous wavelet transform. The developed spectrophotometric methods exploit the characteristic spectral differences between dolutegravir and lamivudine in order to quantify them simultaneously. These methods have shown promising results in terms of sensitivity and selectivity as validated per the ICH guidelines. Moreover, these methods offer a straightforward and economical alternative to more intricate analytical methodologies like high-performance liquid chromatography. By incorporating the analytical eco-scale and AGREE for greenness evaluation of the proposed methods, we can further ensure that these techniques are effective and environmentally friendly, aligning with the principles of green chemistry. This evaluation will provide a comprehensive understanding of the environmental friendliness of these spectrophotometric methods in pharmaceutical analysis.

Derivative spectroscopy and wavelet transform as green spectrophotometric methods for abacavir and lamivudine measurement

Herein, two different sustainable and green signal processing spectrophotometric approaches, namely, derivative spectroscopy and wavelet transform, have been utilized for effective measurement of the antiretroviral therapy abacavir and lamivudine in their pharmaceutical formulations. These methods were used to enhance the spectral data and differentiate between the absorption bands of abacavir and lamivudine in order to accurately measure their concentrations. For determining abacavir and lamivudine, the first derivative spectrophotometric method has been applied to the zero-order and ratio spectra of both drugs. The same approach has been tested using the continuous wavelet transform method where a second order 2.4 of rbio and bior wavelet families were found to be optimum for measuring both drugs. Validation of the proposed methods affirmed their reliability in terms of linearity over the concentration range 1.5–30 µg/mL and 1.5–36 µg/mL for abacavir and lamivudine, respectively, precision (RSD < 2 %), and accuracy with mean recoveries ranging between 98 % and 102 %. Additionally, these spectrophotometric methodologies were applied to real pharmaceutical preparations and yielded results congruent with a prior chromatographic method. Most prominently, the proposed methods stood out for their greenness and sustainability with 97 points as evaluated by the analytical eco-scale method and a score value of 0.79 as analyzed by AGREE method, thereby making them suitable for resource-limited settings and highlighting the potential for broader application of green analytical methods in pharmaceutical analysis.

Mogućnost zamene konvencionalnih organskih rastvarača zelenim dubokim eutektičkim rastvaračima u analitici lekova

In recent years, Deep Eutectic Solvents (DESs) have attracted increasing attention in various scientific disciplines. Their unique properties, such as low toxicity, biodegradability, low cost and versatility, have made them an attractive alternative to conventional organic solvents. In pharmaceutical analysis, where the demand for environmentally friendly methods is growing, questions regarding whether DESs can replace organic solvents as "green solvents" have arisen. This paper explores the potential applications of DESs in drug analysis, and highlights the benefits and challenges they bring. Examples of the use of DESs in chromatographic techniques and in the extraction of drugs from various samples are presented. Additionally, research on the stability and toxicity of DESs in analytical applications is discussed. Based on the available data, it could be concluded that DESs have the potential to become an important component of analytical methods in pharmaceutical analysis and provide environmentally sustainable and efficient alternatives to conventional organic solvents. However, further research is needed to better understand their properties and optimize their application in drug analysis.

Multi-spectroscopic assay methods for concurrent determination of recent anti-gout combination, a comparative study

Recently, Chemometric calibration methods in spectrophotometric analysis are achieving significant attention in the quality control of resolving drug mixtures and pharmaceutical formulations containing two or more drugs with overlapping spectra. The simple univariate methods have been used over the last few decades and has proven to be highly efficient and easy to apply. In this study, a comparative study was performed between some univariate and multivariate methods to determine if chemometric methods can substitute univariate methods in pharmaceutical analysis. In this study, three chemometric techniques were compared to seven univariate techniques to resolve a mixture of mefenamic acid and febuxostat in their raw materials, dosage forms and spiked human plasma. Mefenamic acid and febuxostat were used together for treatment of gout. The applied chemometric methods are partial least squares (PLS), artificial neural network (ANN) and genetic algorithm partial least squares (GA-PLS), while the used univariate methods include first derivative, second derivative, ratio spectra, derivative ratio spectra, ratio subtraction, Q-Absorbance ratio and mean centering spectrophotometric methods. The ten proposed methods were found to be green, sensitive, and rapid. They are simple and did not require any pre-separation steps. The results of both univariate and multivariate approaches were statistically compared with the reported spectrophotometric methods using student’s t test and ratio variance F-test. They were also compared with each other, using one-way analysis of variance (ANOVA). These methods were assessed and validated according to ICH guidelines. The studied drugs were analyzed in their pharmaceutical dosage forms and spiked human plasma with good recoveries using the developed methods, which qualify them for routine quality control of the studied drugs.

Spectrometric methods in pharmaceutical analysis of glycosaminoglycans: the state-of-the-art

Glycosaminoglycans are important complex carbohydrates that are used in a number of pharmaceutical products. Because glycosaminoglycans are obtained by isolation from biological materials, their pharmaceutical analysis before therapeutic use is of paramount importance. Due to their versatility, wide applicability, non-destructiveness, and in particular the possibility of obtaining a “fingerprint” clearly proving the given chemical specie, spectrometric methods are one of the essential methods used for these analyzes. This review is focused on significant spectrometric methods used in the pharmaceutical analysis of glycosaminoglycans. The advantages and prospects of individual methods (NMR spectrometry, infrared and Raman spectrometry, UV/Vis spectrometry, spectrofluorimetry, chemiluminescence, and circular dichroism) used and methodological aspects of the analysis are discussed. The possibilities of further development and application of spectral methods in the discussed area are outlined.

Recent advances in capillary electrophoretic migration techniques for pharmaceutical analysis

Since the introduction about 30 years ago, CE techniques have gained a significant impact in pharmaceutical analysis. The present review covers recent advances and applications of CE for the analysis of pharmaceuticals. Both small molecules and biomolecules such as proteins are considered. The applications range from the determination of drug-related substances to the analysis of counterions and the determination of physicochemical parameters. Furthermore, general considerations of CE methods in pharmaceutical analysis are described.

Rapid and Sensitive CZE Method for Quality Control Analysis of Pharmaceuticals Containing Pseudoephedrine, Triprolidine and Paracetamol

A rapid and sensitive CZE (Capillary Zone Electrophoresis) method for pharmaceutical analysis was developed and fully validated. The active compounds: Pseudoephedrine hydrochloride (PSE), Triprolidine hydrochloride (TRI) and Paracetamol (PAR) were separated and quantitatively determined using the tris-borate 30 mM buffer at pH = 9.0 as a Background Electrolyte (BGE). The electrophoretic separation was carried out at 25 kV in an unmodified fused silica capillary of I.D. = 50 μm with a “bubble-cell” for UV detection at 210 nm and 25°C. The separation was reached in about 3 min. After calibration the method was applied for analysis of three commercially available pharmaceutical preparations. The repeatability (RSD%) of migration time (tm) was ranging between 0.47% and 0.90% and of peak areas (A) between 0.63% and 3.64%. The Limit of Detection (LOD) values was of 0.19 μg/mL, 0.31 μg/mL and 0.08 μg/mL for respectively PSE, TRI and PAR. The results obtained in this study showed that the proposed method was useful in routinely analysis of pharmaceuticals.

Pre-Validation and Performance Prediction Using Pressure Monitoring to Evaluate HPLC Method Development Changes

HPLC methods for pharmaceutical analysis evolve from method development to commercial product testing. The majority of development and validation takes place in an RD however, the system pressure increases over time. These underlying data indicate a potential trend prior to method validation. As a result, sample preparation and HPLC condition modifications are evaluated using pressure plots as a key performance metric.

The paradigm shifting role of chromatographic methods in pharmaceutical analysis

An overview is presented of the impact of chromatographic method developments on the quality control of pharmaceuticals as of the 1950s up until the present times. This survey is mainly based on the changes in pharmacopeias starting with United States Pharmacopeia (USP) 16, issued in 1960, up to the presently effective USP 34 and European Pharmacopeia 7.2. At the beginning of this period the role of chromatographic methods was negligible and was restricted to classical column chromatography and paper chromatography. However, the invention of high-performance liquid chromatography (HPLC) initiated a rapid paradigm shift in the attitude toward, and the use of, chromatographic methods. As a result, HPLC began a "career" of rapid spreading and development, and by now has undoubtedly become the principal method in pharmaceutical analysis. Likewise, the role of thin-layer chromatography (TLC) and to a lesser extent gas chromatography is also remarkable. The role of these and electrophoretic methods in the identification, assay and purity check of drugs and drug products in the modern pharmacopeias is discussed. As a case study the stability investigation of Depersolone® injection carried out in the 1960s and 35 years later is presented and the information obtainable from the classical and modern approach is compared.

Analytical Validation of Quantitative High-Performance Liquid Chromatographic Methods in Pharmaceutical Analysis: A Practical Approach

Analytical validation is an essential component in allowing a laboratory to ensure routine acceptable performance of analytical methods. Despite the considerable amount of important published work on this subject, diversity still prevails in the employed methodologies because validation of an analytical method depends on the specific purpose of that method. This can lead to difficulties in validation approaches and the interpretation of results. Aiming to assist in the planning of validation methods, we discuss relevant approaches of various parameters in quantitative high-performance liquid chromatographic methods and validation fields in pharmaceutical analysis. Moreover, this article provides several up-to-date examples that should be useful as an introduction to analytical validation for practical applications in academic research or the industrial sector.

HILIC methods in pharmaceutical analysis

In this review, hydrophilic interaction liquid chromatographic (HILIC) applications for pharmaceutical analysis are discussed. The HILIC technique uses an aqueous/organic modifier mobile phase with a high organic modifier fraction and a hydrophilic stationary phase (SP). In general, the SPs are silica or polymer based. The silica-based columns are most often applied and are divided into bare-silica particle, chemically bonded silica particle, and monolithic phases. The bare-silica columns are most frequently used. The much less applied polymer-based columns are also divided into particle and monolithic phases. In this review, the applications are grouped and discussed according to the SP type used. Whenever possible, the considered HILIC application is compared with other HILIC methods, e.g. on other SPs, and/or with other separation modes, for that application. The advantages and drawbacks of HILIC are also discussed, as well as the method validation issues, when executed.

The role of assay methods in characterizing the quality of bulk pharmaceuticals.

This study presents the role of assay methods in characterizing the quality of bulk substances in pharmaceutical analysis. High-performance liquid chromatography (HPLC) is the most remarkable development and the technique has become very significant in the quality control of bulk drugs and pharmaceutical formulations, even at the pharmacopoeial level. Development of HPLC and other chtromatographic techniques, coupled with mass spectrometry, is also useful in the determination of drugs and their metabolites in biological samples. The role of electrophoretic, spectroscopic, and other methods in pharmaceutical analysis are discussed here. There are separate sections devoted to microscopy techniques that are useful in the pharmaceutical field, as also the regulatory aspects of drug analysis, with emphasis on questions related to validation.

On-line solid phase extraction LC–MS/MS analysis of pharmaceutical indicators in water: A green alternative to conventional methods

A method using automated on-line solid phase extraction (SPE) directly coupled to liquid chromatography/tandem mass spectrometry (LC–MS/MS) has been developed for the analysis of six pharmaceuticals by isotope dilution. These selected pharmaceuticals were chosen as representative indicator compounds and were used to evaluate the performance of the on-line SPE method in four distinct water matrices. Method reporting limits (MRLs) ranged from 10 to 25 ng/L, based on a 1 mL extraction volume. Matrix spike recoveries ranged from 88 to 118% for all matrices investigated, including finished drinking water, surface water, wastewater effluent and septic tank influent. Precision tests were performed at 50 and 1000 ng/L with relative standard deviations (RSDs) between 1.3 and 5.7%. A variety of samples were also extracted using a traditional off-line automated SPE method for comparison. Results for both extraction methods were in good agreement; however, on-line SPE used approximately 98% less solvent and less time. On-line SPE coupled to LC–MS/MS analysis for selected indicators offers an alternative, more environmentally friendly, method for pharmaceutical analysis in water by saving time and costs while reducing hazardous waste and potential environmental pollution as compared with off-line SPE methods.

Principles and Techniques of Electroanalytical Stripping Methods for Pharmaceutically Active Compounds in Dosage Forms and Biological Samples

A review of the applications, principles, advantages of stripping voltammetric techniques, namely anodic, cathodic, abrasive, adsorptive stripping voltammetry and potentiometric stripping analysis is presented. Stripping voltammetric methods in pharmaceutical analysis are discussed and the generally applicable procedure is given. The use and advantages and disadvantages of these techniques at different electrodes are discussed. The analytical applications of stripping techniques to pharmaceutically active compounds are also discussed. Various selected determination studies on drugs by stripping techniques from pharmaceutical dosage forms and biological samples are reviewed. Keywords: Adsorptive stripping, Anodic stripping, Biological samples, Cathodic stripping, Determination, Potentiometric stripping, Drugs

Electrophoretic methods in pharmaceutical analysis

Electrophoretic methods in pharmaceutical analysis

Strategic approach for method selection in high-performance liquid chromatography

A strategic approach for the selection of high-performance liquid chromatographic methods in pharmaceutical analysis is outlined. Firstly, on the basis of the acid-base properties of the solute (s) and its hydrophobicity (as reflected by its log P value or total number of carbons), a battery of Chromatographic methods is selected. This battery of methods contains first choice, second choice and excluded methods. The Chromatographic modes considered are reversed-phase, normal-phase, gradient elution and ion-pair. Afterwards, on the basis of a structure-retention relationship, initial solvent strength conditions (i.e., the percentage of the organic modifier in the mobile phase) can be chosen in the reversed-phase and normal-phase mode corresponding to the chromatographers' needs.

Planar chromatography: Current status and future perspectives in pharmaceutical analysis — I. Applicability, quantitation and validation

The most important features of capillary action planar chromatographic methods are summarized. Certain properties such as case in operation, sensitivity to experimental conditions, stationary and mobile phase selection, phase system optimization, separation efficiency and detection possibilities are discussed only briefly. Other aspects such as the applicability of planar chromatographic methods in pharmaceutical analysis, quantitation and validation are considered in more detail. The advantages and limitations of different evaluation techniques (visual comparison, spot elution techniques and in situ densitometry) are also discussed. Validation steps specific to planar chromatographic methods are emphasized.

The use of solution thermochemistry in quality control methods in pharmaceutical analysis

Some of the procedures that have been reported for the determination of the active ingredients in dosage forms of some ethical pharmaceutical products are reviewed. The requirements of methods for quality control and the advantages of using thermochemical methods to achieve them are discussed.

Selection of high-performance liquid chromatographic methods in pharmaceutical analysis : IV. Selection of most applicable separation system

Different analytical tasks in the pharmaceutical analysis can be classified according to the separation problems into three main groups: trace analysis, assay methods and separation of closely related compounds including isomers. The most important requirements of high-performance liquid chromatographic (HPLC) methods with respect of the separation problems are summarized. Considerations and recommendations for the selection of the most applicable HPLC system to solve particular analytical problems are discussed. HPLC methods can be compared on the basis of the system resolution (SR) and system selectivity (SS). Criteria developed for the characterization of HPLC methods considering the difficulties created by the different analytical problems are established. The principles of the selection of the most applicable separation systems are demonstrated through some practical examples in pharmaceutical analysis.

Selection of high-performance liquid chromatographic methods in pharmaceutical analysis : III. Method validation

The most important steps in the validation of high-performance liquid chromatographic (HPLC) methods are discussed. The establishment of system suitability data and the assessment of peak purity are demonstrated on the example of bisquaternary amino steroids. For the recognition of incomplete resolution of adjacent peak pairs, the absorbance-ratio method in which the ratio of absorbances at two preselected wavelengths are plotted as a function of time in combination with the separation of sample components subjected to various chemical and physico-chemical treatments (stress conditions) is applied. The separation power and performance of the HPLC systems are characterized by the system resolution (SR) and system selectivity (SS). The special demands of stability-indicating methods are summarized.