Discrimination and analytical profiling of colored printed documents using ATR-FTIR spectroscopy coupled with explorative and predictive statistical analysis: Part I.

Printed documents are a common form of evidence in forensic document examination. The integration of spectroscopy with chemometrics have evolved evidential analytical interpretation of printing inks. However, we report the first ever study that explores the examination of both black and colored printed documents combined with explorative Principal Component Analysis (PCA) and supervised techniques viz. Soft independent modelling of class analogy (SIMCA) and Partial Least Square- Discriminant Analysis (PLS-DA). The study investigated 74 (40 Ink-based and 34 Toner- based) colored printed document samples using ATR-FTIR to discriminate and determine the source of origin of an unknown printed document using a non-destructive approach. Qualitative analysis by ATR- FTIR indicated the presence of polystyrene, bisphenol A and acrylates as the common binder polymers in the samples. The study was also able to obtain pigment information like presence of PR 57 and PR 146 in magenta, Carbon black in black, Copper Phthalocyanine and PB 15 in Cyan and PY 74 in yellow colored printed samples. Further, PCA has been used as an explorative technique that showed a variance of 97 % in the dataset and indicating that the color Cyan contributes to the maximum classification accuracy. SIMCA has been used as a supervised method to classify the known and test samples to their respective defined classes. However, SIMCA could only classify Toner-based samples in their respective class and inconclusive results were obtained in case of Ink-based samples. Finally, PLS-DA was also used to classify the two class of samples which resulted in a discrimination accuracy of 98.6 %. The derived model was also used for validation study on blind test samples which provided 100 % classification results.

Exploring the effect of surfactants on the interactions of manganese dioxide nanoparticles with biomolecules.

Interactions of manganese dioxide nanoparticles (MnO2 NPs) with vital biomolecules namely deoxyribonucleic acid (DNA) and serum albumin (BSA) have been studied in association with different surfactants by using fluorescence (steady state, synchronous and 3D), UV-visible, resonance light scattering (RLS), dynamic light scattering (DLS), and sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE). The esterase activity of serum albumin was tested in associations with MnO2 NPs and surfactants. The antioxidant potential of prepared NPs was also evaluated (DPPH method). Gel electrophoresis was carried out to analyze the effect of MnO2 NPs and surfactants on DNA. Presence of CTAB, Tween 20, DTAB and Tween 80 enhanced nanoparticle-protein binding. Tween 20 based nanoparticle systems showed long-term stability and biocompatibility. The quenching of BSA fluorescence emission in presence of MnO2 NPs alone and along with Tween 20 revealed stronger association of nanoparticles with proteins. Enhancement in the esterase activity (BSA) was observed in the presence of Tween 20. Furthermore, radical scavenging activity showed highest antioxidant potential in presence of Tween 20. The enthalpy and entropy assessment for protein-NPs association showed the predominance of Vander Waals interactions and hydrogen bonding. The synchronous fluorescence analysis highlighted the involvement of tryptophan (Trp) in the MnO2 NPs-protein interactions. The study evaluates the influence of surfactant on the associations of MnO2 NPs with the essential biomolecules. The findings can be crucially utilized in designing biocompatible MnO2 formulations for long term applications.Communicated by Ramaswamy H. Sarma.

Evaluation of the antiglycating potential of thymoquinone and its interaction with BSA.

Thymoquinone (TQ) is a bioactive component of medicinal plant, Nigella sativa. It has been identified as promising anti-inflammatory and anti-analgesic properties. In the present study, the TQ has been investigated for physiological interaction as well as binding properties with serum albumin and their thermodynamic parameters at different temperatures. Glycation process was checked with the measurement of fructosamine content, carbonyl content and total advanced glycated end products. The aggregation of amyloid ß-structure was measured with Thioflavin-T and the secondary structure of BSA was observed by circular dichroism (CD) in glycated and thermal treated samples. The results indicate that the TQ showed binding interaction (both static and dynamic) with BSA (Kb= 18.31 × 107 M-1 at 293 K) and suppression of glycated products. The glycation-induced and thermal aggregation were prevented and the secondary structure of BSA was maintained. Therefore, these findings suggest that TQ may be used for a therapeutic drug for antiglycation as well as anti-aggregation.Communicated by Ramaswamy H. Sarma.

Influence of surfactants on biomolecular conjugation of magnetic nanoparticles.

Here, we report the physicochemical interaction among iron oxide nanoparticles (MNPs) and essential biomolecules, namely, serum albumin (BSA, HSA), collagen and deoxyribonucleic acid (DNA) in the presence of various cationic, anionic and non-ionic surfactants. Iron oxide nanoparticles are synthesized by the wet chemical process and are characterized by X-ray powder diffraction analysis (XRD), Fourier transform infrared spectroscopic, UV-Vis spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy mapping studies . The conjugation of MNPs protein was analyzed using UV-Vis spectroscopy, fluorescence spectroscopy, circular dichroism technique and gel electrophoresis. The spectroscopic investigation illustrates the surfactant-dependent binding between MNPs and protein. Gel electrophoresis in the absence and presence of MNPs-surfactant systems has been used to study the impact on DNA structure. It was found that Tween 80 imparts better stability as well as biocompatibility to the synthesized MNPs. The findings offer extensive information on the influence of various surfactant coatings on MNP surfaces and their influence on vital biomolecules, making it useful for designing MNPs for biological applications.Communicated by Ramaswamy H. Sarma.

Studies on the antiglycating potential of zinc oxide nanoparticle and its interaction with BSA.

Nanoparticles have been proven to be a great tool as bio-sensors, medical therapeutic agents and drug delivery vehicles. In this study, the chemically synthesized zinc oxide nanoparticles (ZnO NPs) have been characterized with UV-spectrophotometer, FTIR, XRD, TEM and DLS. These ZnO NPs were investigated with respect to their binding interaction with serum albumin and the thermodynamic parameters of these interactions at different temperatures. Glycation process was checked in the presence of ZnO NPs by measuring fructosamine and carbonyl content for glycated end products and aggregation by Congo red assay. The intrinsic activities of bovine serum albumin (BSA) like esterase and cysteine reactivity were also evaluated in the presence of ZnO NPs. The results indicate that the ZnO NPs showed static as well as dynamic binding interaction with BSA, reduced the content of glycation products and prevented the glycation induced aggregation and antioxidant properties. Therefore, these findings suggest that ZnO NPs may be used for drug delivery agents and antiglycating as well as an antioxidant agent.Communicated by Ramaswamy H. Sarma.

Biotransformation of xenobiotics by hairy roots.

The exponential industrial growth we see today rides on the back of large scale production of chemicals, explosives and pharmaceutical products. However, the effluents getting released from their manufacturing units are greatly compromising the sustainability of our environment. With greater awareness of the imperative for environmental clean-up, a promising approach that is attracting increasing research interests is biodegradation of xenobiotics. In this approach, biotransformation has proven to be one of the most effective tools. While many different model frameworks have been used to study different aspects of biotransformation, hairy roots (HRs) have been found to be exceptionally valuable. HR cultures are preferred over other in-vitro model systems due to their biochemical stability and hormone-autotrophy. In addition, the multi-enzyme biosynthetic potential of HRs which is similar to the parent plant and their relatively low-cost cultural requirements further characterize their suitability for biotransformation. The recent progress observed in scale-up of HR cultures and understanding of functional genomics has opened up new dimensions providing valuable insights for industrial application. This review article summarizes the potential of HR cultures in the biotransformation of xenobiotics, their limitations in the application on a large scale and current strategies to alleviate them. Advancement in bioreactors engineering enabling large scale cultivation and modern gene technologies improving biotransformation efficiency promises to extend laboratory results to industrial applications.

Insights into the Interactions of Sulfamethoxazole with Organized Assemblies of Ionic and Nonionic Surfactants.

This work reports the physicochemical behavior of antibiotic drug sulfamethoxazole (SMX) in the presence of different surfactants, viz., cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide, sodium dodecyl sulfate, sodium deoxycholate, Tween 80, and Tween 20. The drug-surfactant systems were studied by UV-visible and fluorescence spectroscopies to assess the binding constants ( Kb), partition coefficient ( Kx), free energy of partition (Δ Gp), aggregation number ( Nagg), and quenching constant ( KSV). Solubilization studies were carried out to understand the encapsulation efficiency of the system, which was found to increase as a function of CTAB concentration. Surface tension measurements enabled us to determine the change in critical micelle concentration as well as to calculate the variation in surface parameters of surfactant in the presence of drug, viz., surface pressure (π), surface excess concentration (γmax), and minimum area ( Amin). In addition, UV-visible, fluorescence, and circular dichroism studies were carried out to check the effects of surfactant-based SMX formulation on serum proteins.

Mechanistic insights into the interactions of magnetic nanoparticles with bovine serum albumin in presence of surfactants.

This work reports the physicochemical parameters and the nature of association between magnetic nanoparticles and bovine serum albumin (BSA) in presence of cationic and anionic surfactants. Magnetic iron oxide nanoparticles (MNPs) are first synthesized using chemical co-precipitation method and subsequently characterized by FTIR, XRD, DLS, TEM and Zeta potential. The bare nanoparticles are then coated with BSA and their interactions studied using fluorescence spectroscopy, dynamic light scattering and circular dichroism techniques. The spectroscopic investigation sheds light into various aspects of binding and size variation during the molecular association of BSA with the MNPs in absence and presence of cationic and anionic surfactants. Isothermal titration calorimetry was used to probe the thermodynamic parameters of the systems. MNPs-BSA system was found to be more stable in presence of cationic surfactant. This study provides valuable mechanistic insights into the interactions taking place at the interface of the nanoparticles which further helps in designing a stable colloidal MNPs systems.

Cellular internalization and detailed toxicity analysis of protein-immobilized iron oxide nanoparticles.

Iron oxide nanoparticles (IONPs) have been extensively used for biomedical applications like in the diagnosis and treatment of various diseases, as contrast agents in magnetic resonance imaging, and in targeted drug delivery. Despite several attempts, there is a dearth of information with respect to the cellular response and in-depth toxicity analysis of the nanoparticles. Considering the potential benefits of IONPs, there is a need to study the potential cellular damage associated with IONPs. The size and surface of the particles are some critical factors that should be analyzed when evaluating cytotoxicity. Therefore, in this study, we synthesized and characterized bare (7-9 nm) and protein-coated IONPs of diameter 50-70 nm, and evaluated their toxicity on membrane integrity, intracellular accumulation of reactive oxygen species, and mitochondrial activity in mouse fibroblast cell line by lactate dehydrogenase, 2',7'-dichlorofluorescein diacetate, and [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] (MTT) assays, respectively. Our extensive cytotoxicity analysis demonstrated that the size of the IONPs and their surface coating are the critical determinants of cellular response and potential mechanism toward cytotoxicity. The study of the interactions and assessment of potential toxicity of the nanoparticles with cells/tissues is a key determinant when considering their translation in biomedical applications.