Attenuated Total-reflection Fourier-transform Spectroscopy Research Articles

New Iron(III)-Containing Composite of Salinomycinic Acid with Antitumor Activity—Synthesis and Characterization

In this study we demonstrated for the first time synthetic procedures for composites of salinomycin (SalH) and two-line ferrihydrite. The products were characterized by various methods such as elemental analysis, attenuated total reflectance–Fourier-transform spectroscopy (ATR-FTIR), electron paramagnetic resonance spectroscopy (EPR), powder X-ray diffraction analysis (XRD), electrospray-ionization mass spectrometry (ESI-MS), thermogravimetric analysis with differential thermal analysis (DTA) and mass spectrometry (TG-DTA/MS). The EPR spectra of the isolated compounds consisted of signals associated with both isolated Fe3+ ions and magnetically coupled Fe3+ ions. Powder XRD analyses of the isolated products showed two intense and broad peaks at 9° and 15° 2Θ, corresponding to salinomycinic acid. Broad peaks with very low intensity around 35°, assigned to two-line ferrihydrite, were also registered. Based on the experimental results, we concluded that salinomycin sodium reacted with Fe(III) chloride to form composites consisting of two-line ferrihydrite and salinomycinic acid. One of the composites exerted pronounced antitumor activity in the sub-micromolar concentration range against human cervical cancer (HeLa), non-small-cell lung cancer (A549), colon cancer (SW480), and ovarian teratocarcinoma (CH1/PA1) cells.

Isolation and Characterization of Indigenous Ureolytic Bacteria from Mindanao, Philippines: Prospects for Microbially Induced Carbonate Precipitation (MICP)

Microbially induced carbonate precipitation (MICP), a widespread phenomenon in nature, is gaining attention as a low-carbon alternative to ordinary Portland cement (OPC) in geotechnical engineering and the construction industry for sustainable development. In the Philippines, however, very few works have been conducted to isolate and identify indigenous, urease-producing (ureolytic) bacteria suitable for MICP. In this study, we isolated seven, ureolytic and potentially useful bacteria for MICP from marine sediments in Iligan City. DNA barcoding using 16s rDNA identified six of them as Pseudomonas stutzeri, Pseudomonas pseudoalcaligenes, Bacillus paralicheniformis, Bacillus altitudinis, Bacillus aryabhattai, and Stutzerimonas stutzeri but the seventh was not identified since it was a bacterial consortium. Bio-cementation assay experiments showed negligible precipitation in the control (without bacteria) at pH 7, 8, and 9. However, precipitates were formed in all seven bacterial isolates, especially between pH 7 and 8 (0.7–4 g). Among the six identified bacterial species, more extensive precipitation (2.3–4 g) and higher final pH were observed in S. stutzeri, and B. aryabhattai, which indicate better urease production and decomposition, higher CO2 generation, and more favorable CaCO3 formation. Characterization of the precipitates by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) confirmed the formation of three carbonate minerals: calcite, aragonite, and vaterite. Based on these results, all six identified indigenous, ureolytic bacterial species from Iligan City are suitable for MICP provided that the pH is controlled between 7 and 8. To the best of our knowledge, this is the first report of the urease-producing ability and potential for MICP of P. stutzeri, P. pseudoalcaligenes, S. stutzeri, and B. aryabhattai.

The characteristics and biological activity enhancements of melatonin encapsulations for skin care product applications

Melatonin (MLT) exhibits antioxidant, ultraviolet protection, anti-inflammatory, and anti-aging properties. However, its effectiveness is limited by instability, a short half-life, and incompatible absorption. In this research, we encapsulated melatonin (MLT) in transfersomes (MT) and niosomes (MN) to enhance their properties and investigate their effects through in vitro cell assays using murine macrophages cells and human foreskin fibroblasts cells. The vesicle morphology, vesicle size, polydispersity index, zeta potential, entrapment efficiency (EE%), attenuated total reflectance-Fourier transform spectroscopy (ATR-FTIR) spectra, along with in vitro release, permeation profiles, and stability study were also evaluated. The results showed that both encapsulations displayed spherical morphology at the nanometric scale, their great physical stability and provided an EE% range of 58–78%. The MLT incorporation into the vesicle was confirmed by the ATR-FTIR spectra. Additionally, the encapsulation’ release profiles fitted with the Higuchi model, indicating controlled release of melatonin. Furthermore, MT showed greater permeability than MN and MS including melatonin deposition. In cell assays, MT exhibited significantly higher nitric oxide inhibition and stimulation of collagen compared to MN and MS. Therefore, MT demonstrated the highest possibility for anti-inflammatory and collagen-stimulating activities that could be applied in pharmaceutical or anti-aging cosmetic products.

Selective anomer crystallization from aqueous solution: Monitoring lactose recovery under mutarotation limitation via attenuated total reflection Fourier-transform spectroscopy and theoretical rate analysis

Lactose is typically produced via cooling crystallization either from whey or whey permeate (edible grade) or from aqueous solution (pharmaceutical grade). While in solution, lactose is present in 2 anomeric forms, α- and β-lactose. During cooling crystallization under standard process conditions, only α-lactose crystallizes, depleting the solution of α-anomer. In practice, mutarotation kinetics are often assumed to be much faster than crystallization. However, some literature reports limitation of crystallization by mutarotation. In the present research, we investigate the influence of operating conditions on mutarotation in lactose crystallization and explore the existence of an operation regimen where mutarotation can be disregarded in the crystallization process. Therefore, we study crystallization from aqueous lactose solutions by inline monitoring of concentrations of α- and β-lactose via attenuated total reflection Fourier-transform spectroscopy. By implementing a linear cooling profile of 9 K/h to a minimum temperature of 10°C, we measured a remarkable increase in β/α ratio, reaching a maximum of 2.19. This ratio exceeds the equilibrium level by 36%. However, when the same cooling profile was applied to a minimum temperature of 25°C, the deviation was significantly lower, with a maximum β/α ratio of 1.72, representing only an 8% deviation from equilibrium. We also performed a theoretical assessment of the influence of process parameters on crystallization kinetics. We conclude that mutarotation needs to be taken into consideration for efficient crystallization control if the crystal surface area and supersaturation are sufficiently high.

A label-free electrochemical immunosensor based on 11-mercaptoundecanoic acid grafted chitosan and poly(N-methylaniline) for the detection of carcinoembryonic antigen

Carcinoembryonic antigen (CEA) is a cancer marker used for monitoring cancer treatment. Herein, a label-free electrochemical immunosensor for determining CEA concentration composed of the thiolated chitosan (tCHI) and the doped poly(N-methylaniline) (dPNMA) is proposed. The tCHI served as a support matrix for the immobilization of CEA antibodies (anti-CEA) and was prepared by using 11-mercaptoundecanoic acid (MUA) as a grafting agent on chitosan (CHI). The excellent electrical conductivity of the dPNMA was utilized as an electron transfer layer for the proposed immunosensor. The successful preparation of the tCHI was confirmed by the attenuated-total reflection Fourier transform spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were used to illustrate the performance of the proposed immunosensor. The determination of CEA concentration was relied on the decrease in the DPV current response with increasing CEA concentration from the creation of the antigen–antibody immunocomplex. The proposed immunosensor demonstrated a broad concentration range of 0.01 to 30 ng mL−1 with a low limit of detection (LOD) of 0.01 ng mL−1. In addition, the present sensor exhibited excellent selectivity, reproducibility, and long-term stability, suggesting its potential use to determine CEA in clinical immunoassay.

Fabrication and characterization of chitosan-polycaprolactone core-shell nanofibers containing tetracycline hydrochloride

Chitosan-polycaprolactone (CS-PCL) core-shell structured nanofibers, in which CS and PCL respectively form the core and shell layers, were electrospun by coaxial electrospinning method. In this regard, three sets of core-shell nanofiber samples were prepared and the best one with desirable morphology, smooth surface, and without beads was characterized. Then tetracycline hydrochloride (TCH) is embedded in the CS core. An attempt has been made to prove the formation of the core-shell structure and encapsulation of the drug by water contact angle (WCA) measurements and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR). Transmission electron microscopy (TEM) was also used for the validation of the core-shell structure. Morphological investigations were conducted using scanning electron microscopy (SEM) which showed smooth CS-PCL nanofibers without any beads and with an average diameter of 285 ± 75 nm. Compositional analysis was carried out by differential scanning calorimetry (DSC) which indicated that about 64.3% of the prepared CS-PCL core-shell nanofibers were composed of PCL constituent. Also, In-vitro degradation of the nanofibers in the Phosphate Buffered Saline (PBS) solution was evaluated. In comparison to the blend nanofibers, TCH-loaded CS-PCL core-shell nanofibers showed a two-stage release of the drug, an initial burst release stage followed by a sustained release. Moreover, the antibacterial activity of CS-PCL core-shell nanofibers loaded with TCH was confirmed; hence, it has some potential applications in biomedical areas such as in wound dressing and drug delivery systems.

Fresh, freeze-dried or cell wall samples: Which is the most appropriate to determine chemical, structural and rheological variations during apple processing using ATR-FTIR spectroscopy?

Attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) was applied on fresh (NF), freeze-dried (FD) and cell wall materials (AIS) of raw and processed apples. These samples prepared from 36 apple sets and the corresponding 72 purees, issued from different varieties, agricultural practices, storage periods and processing conditions, were used to build models including exploratory analysis, supervised classification and multivariate calibration. Fresh and freeze-dried samples presented similar fingerprint spectral variations due to processing. ATR-FTIR directly on fresh purees satisfactorily predicted textural properties such as particle average size and volume (RPD>3.0), while freeze-drying improved assessment of chemical (RPD>3.2) and rheological (RPD>3.1) parameters using partial least-squares regression. The assessment of texture and macrocomponents of purees can be obtained with a limited sample preparation. For research applications because of a need of sample preparation, changes of cell wall composition during fruit processing could be assessed in relationship with pectin degradation.

Co-electrospun poly(lactic acid)/gelatin nanofibrous scaffold prepared by a new solvent system: morphological, mechanical and in vitro degradability properties

Poly(lactic acid)-gelatin (PLA-GT) core-shell nanofibers were prepared successfully via coaxial electrospinning method using new solvents for dissolving core and shell polymers, dimethylformamide for dissolving PLA and concentrated acetic acid for dissolving gelatin. Transmission electron microscopy (TEM) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) were used to confirm the formation of core-shell structure in the nanofibers with these new solvents. Morphological investigation of the as-spun nanofibers was carried out using scanning electron microscopy (SEM) which revealed a bead-free ribbon-like morphology for PLA-GT core-shell structured nanofibers with an average diameter of 347 ± 88 nm. Although compositional analysis by differential scanning calorimetry (DSC) indicated that PLA content in the prepared core-shell nanofibers was low (approximately 7.8%), the PLA presence in the nanofibers’ core could improve their mechanical properties. The nanofibers’ shell was crosslinked by glutaraldehyde. In addition to highly preserving nanofibrous and porous structures of the mat, the crosslinking treatment strengthened core-shell nanofibers significantly. In vitro degradation test showed that even after 11 days, the fibrous structure of crosslinked core-shell mat was maintained. The fabricated PLA-GT core-shell nanofibers have potentials in some biomedical applications.

Preparation and characterization of electrospun poly(lactic acid)-chitosan core-shell nanofibers with a new solvent system

Poly(lactic acid)-chitosan (PLA-CS) core-shell nanofibers were successfully fabricated by coaxial electrospinning technique using a new solvent system for the core and shell solutions, dimethylformamide for the core solution and trifluoro-acetic acid/acetic acid (90/10 v/v) for the shell solution. The formation of the core-shell structure of the nanofibers with this new solvent system was confirmed by transmission electron microscopy (TEM) and attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR). Morphology of the as-spun nanofibers was investigated by scanning electron microscopy (SEM) which showed bead-free smooth PLA-CS core-shell type nanofibers with an average diameter of 671 ± 172 nm and a broad diameter distribution. Thermogravimetric analysis (TGA) indicated that although PLA content was less than CS in the core-shell nanofibrous mat (20.7% PLA vs. 39% CS) the presence of PLA in the core of nanofibers significantly improved their mechanical properties. The PLA-CS core-shell nanofibers showed a two-stage release behavior of curcumin drug; an initial burst release followed by a sustained release, when the drug was incorporated in the core layer of nanofibers; hence it has potential applications in some biomedical areas such as wound dressing and drug delivery.

Attenuated total reflectance spectroscopy to diagnose skin cancer and to distinguish different metastatic potential of melanoma cell.

Early diagnosing of skin cancer and investigation of metastatic potential of cancer cells are very important to treat it appropriately. Infrared spectroscopy of biological tissues is an emerging technique which gives the spectral differences between healthy and diseased cells. In this work, we have demonstrated that attenuated total reflectance Fourier transform (ATR-FTIR) spectroscopy can be used in diagnostic of skin cancer and in differentiating metastatic potential of cancer cells. Using IR spectroscopy, we can identify various types of cancer such as basal cell carcinoma, malignant melanoma, nevus and metastatic potential by alternations in hydration level and molecular changes. We examined biopsy of different types of cancer cells to diagnose skin cancer at early stages by using FTIR spectroscopy. To differentiate metastases we examined two human melanoma cells of same patient but at different metastatic potential and two murine melanoma cells with common genetic background but different metastatic potential. Our findings revealed that melanoma changes the permeability of cell membrane and higher metastatic potential is related to the hydration level of cell membrane. Thus, ATR-FTIR spectroscopy is a potential technique to help in early diagnosing of skin cancer and to differentiate different metastatic potentials.

Elucidating the Complex Phase Behavior of a Cocrystal System Containing Two APIs and One Coformer

A method has been developed to determine the phase behavior of a cocrystal system that contains two APIs (active pharmaceutical ingredients) and one coformer. Isoniazid, nicotinamide, and succinic acid (denoted as A, B, and C, respectively, hereafter) can form a ternary cocrystal ABC, along with two binary cocrystals, A2C and B2C, making the phase behavior very complex because of a variety of eutectic points. The phase diagram of such a complex system has never been reported. During experiment, solids of A, B, C, or A2C were added in lots to suspensions of pure ABC cocrystal or a mixture of ABC and another solid phase. Attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR) was used to measure the concentrations of A, B, and C during the process. The constitution of solid phases in suspension at each equilibrium point was determined in a real-time manner by performing mass balance between the liquid and solid phase. Multiple eutectic points in equilibrium with a mixture of ABC and A2C, a mi...

Attenuated Total Reflectance Fourier Transform Spectroscopy (ATR-FTIR) and chemometrics for discrimination of espresso coffees with different sensory characteristics

Coffee cup quality, determined by the sensory attributes evaluated by professional tasters, is a decisive factor for evaluating coffee, with the “Specialty Coffee Association of America” (SCAA) classification being nowadays considered the most suitable. Panels of trained coffee tasters are used by the industry to describe and evaluate beverage quality, but those evaluations can be subjective and time demanding. Recent studies have demonstrated the potential of spectroscopy-based methods for establishing parameters of quality in the analysis of food products, including coffee. Thus, the aim of this study was to evaluate the potential of ATR-FTIR and chemometrics to discriminate espresso coffees with different sensory characteristics reported by a panel of coffee tasters. The results showed good consistency among coffee tasters. PLS-DA models based on spectroscopic data were able to classify samples according to sensory attributes, confirming the potential of FTIR and chemometrics in coffee quality evaluation.

Complex refractive index spectra of whole blood and aqueous solutions of anticoagulants, analgesics and buffers in the mid-infrared

Mid-infrared (MIR) spectroscopy is a powerful tool for characterising the vibrations of molecular bonds and is therefore ideal for label-free detection of chemical species. Recent research into thin-film deposition and etching techniques for mid-infrared materials shows potential for realising miniaturised bedside biosensors for clinical diagnostics exploiting MIR spectroscopy, to replace laboratory based-techniques. However, lack of refractive index information for commonly encountered biological media and analytes hampers optimisation of biosensor performance for maximum sensitivity, especially for devices exploiting evanescent spectroscopy. Here we present refractive index data for human whole blood and several aqueous solutions of general interest to the clinical community: anticoagulants, analgesics and buffers. The refractive indices are generally dominated by the water content of each sample and the whole blood spectra exhibit additional strong features due to protein content. Furthermore, we present a generalised method for extracting complex refractive indices of aqueous solutions in the mid-infrared region using conventional attenuated total reflection Fourier transform spectroscopy (ATR-FTIR) without the need for collimated or polarised incident light, as is required for existing methods.

Lanthanide metal–organic frameworks: Structural, thermal and sorption properties

Two coordination polymers of erbium(III) and neodymium(III) ions with 1,3,5-benzenetricarboxylic acid were synthesized under the solvothermal conditions from the dimethylformamide solution. They were characterized by the attenuated total reflectance Fourier transform spectroscopy (ATR-FTIR), thermogravimetry and differential scanning calorimetry (TG-DSC), thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TG-FTIR) and X-ray diffractions methods. The single-crystal X-ray analysis confirmed formation of three-dimensional framework of Er(III) 1,3,5-benzenetricarboxylate with the channels occupied by dimethylformamide and water molecules. Porosity of crystalline complexes was investigated by the nitrogen sorption experiments. The Nd and Er compounds exhibit real porosity with the BET surface area of 259 and 225 m2/g, respectively. The Horvath–Kawazoe analysis of pore-size distributions for the obtained complexes points out to their microporous character.

Structural Effects of Insulin-Loading into HII Mesophases Monitored by Electron Paramagnetic Resonance (EPR), Small Angle X-ray Spectroscopy (SAXS), and Attenuated Total Reflection Fourier Transform Spectroscopy (ATR-FTIR)

Insulin entrapment within a monoolein-based reverse hexagonal (H(II)) mesophase was investigated under temperature-dependent conditions at acidic (pH 3) and basic (pH 8) conditions. Studying the structure of the host H(II) system and the interactions of insulin under temperature-dependent conditions has great impact on the enhancement of its thermal stabilization and controlled release for the purposes of transdermal delivery. Small angle X-ray spectroscopy (SAXS) measurements show that pH variation and/or insulin entrapment preserve the hexagonal structure and do not influence the lattice parameter. Attenuated total reflection Fourier transform spectroscopy (ATR-FTIR) spectra indicate that, although insulin interacts with hydroxyl groups of GMO in the interface region, it is not affected by pH variations. Hence different microenvironments within the H(II) mesophase were monitored by a computer-aided electron paramagnetic resonance (EPR) analysis using 5-doxylstearic acid (5-DSA) as a pH-dependent probe. The microviscosity, micropolarity, order of systems, and distribution of the probes in different microenvironments were influenced by three factors: temperature, pH, and insulin solubilization. When the temperature is increased, microviscosity and order parameters decreased at both pH 3 and 8, presenting different decrease trends. It was found that, at pH 3, the protein perturbs the lipid structure while "pushing aside" the un-ionized 5-DSA probe to fit into the narrow water cylinders. At the interface region (pH 8), the probe was distributed in two differently structured environments that significantly modifies by increasing temperature. Insulin loading within the H(II) mesophase decreased the order and microviscosity of both the microenvironments and increased their micropolarity. Finally, the EPR analysis also provides information about the unfolding/denaturation of insulin within the channel at high temperatures.

Identification of Modified Starches Using Infrared Spectroscopy and Artificial Neural Network Processing

The authentication of food is a very important issue both for the consumers and for the food industry with respect to all levels of the food chain from raw materials to finished products. Corn starch can be used in a wide variety of food preparation as bakery cream fillings, sauce, or dry mixes. There are many modifications of the corn starch in connection with its use in the agrofood industry. This paper describes a novel approach to the classification of modified starches and the recognition of their modifications by artificial neural network (ANN) processing of attenuated total reflection Fourier transform spectroscopy (ATR/FT-IR) spectra. Using the self-organizing artificial neural network of the Kohonen type, we can obtain natural groupings of similarly modified samples on a two-dimensional plane. Such mapping provides the expert with the possibility of analyzing the distribution of samples and predicting modifications of unknown samples by using their relative position with respect to existing clusters. On the basis of the available information in the infrared spectra, a feedforward artificial neural network, trained with the intensities of the derivative infrared spectra as input and the starch modifications as output, allows the user to identify modified starches presented as prediction samples.