UV Absorption Research Articles

The Gas Phase Protonation Sites of Six Naturally Occurring Nicotinoids.

The gas phase protonation sites of six naturally occurring nicotinoids, namely nicotine (NIC), nornicotine (NOR), anabasine (ANB), anatabine (ANT), cotinine (COT), and myosmine (MYO), consisting of a common Pyridine and differing non-Pyridine rings, have been determined for the first time at the physiological temperature from cryogenic ion trap infrared spectroscopy and electronic structure calculations. The protonation site on either of these two rings is related to the nicotinoid's biological activity. At room temperature, NIC is a mixture of Pyridine and Pyrrolidine (non-Pyridine) protomers, whereas NOR, ANB, ANT, and COT are pure Pyridine protomers and finally MYO is mostly a Pyroline (non-Pyridine) protomer. The nearly planar structure of MYO-H+, induced by the presence of a conjugated π system and confirmed from calculations and the UV absorption spectra, breaks from the trends observed for NIC, NOR, and ANB, since its structure is drastically different from the structures of the other nicotinoids.

Sequence-Dependent Surface Coverage of ssDNA Coatings on Single-Wall Carbon Nanotubes.

A combination of experimental measurements and molecular dynamics (MD) simulations was used to investigate how the surfaces of single-wall carbon nanotubes (SWCNTs) are covered by adsorbed ssDNA oligos with different base compositions and lengths. By analyzing the UV absorption spectra of ssDNA-coated SWCNTs before and after coating displacement by a transparent surfactant, the mass ratios of adsorbed ssDNA to SWCNTs were determined for poly-T, poly-C, GT-containing, and AT-containing ssDNA oligos. Based on the measured mass ratios, it is estimated that an average of 20, 22, 26, or 32 carbon atoms are covered by one adsorbed thymine, cytosine, adenine, or guanine nucleotide, respectively. In addition, the UV spectra revealed electronic interactions of varying strengths between the nucleobase aromatic rings and the nanotube π-systems. Short poly-T DNA oligos show stronger π-π stacking interactions with SWCNT surfaces than do short poly-C DNA oligos, whereas both long poly-C and poly-T DNA oligos show strong interactions. These experiments were complemented by MD computations on simulated systems that were constrained to match the measured ssDNA/SWCNT mass ratios. The surface coverages computed from the MD results varied with oligo composition in a pattern that correlates higher measured yields of nanotube fluorescence with greater surface coverage.

Computer-aided drug design supporting sunscreen research: a showcase study using previously synthesized hybrid UV filter-antioxidant compounds.

Although quantum mechanical calculations have proven effective in accurately predicting UV absorption and assessing the antioxidant potential of compounds, the utilization of computer-aided drug design (CADD) to support sustainable synthesis research of new sunscreen active ingredients remains an area with limited exploration. Furthermore, there are ongoing concerns about the safety and effectiveness of existing sunscreens. Therefore, it remains crucial to investigate photoprotection mechanisms and develop enhanced strategies for mitigating the harmful effects of UVR exposure, improving both the safety and efficacy of sunscreen products. A previous study conducted synthesis research on eight novel hybrid compounds (I-VIII) for use in sunscreen products by molecular hybridization of trans-resveratrol (RESV), avobenzone (AVO), and octinoxate (OMC). Herein, time-dependent density functional theory (TD-DFT) calculations performed in the gas phase on the isolated hybrid compounds (I-VIII) proved to reproduce the experimental UV absorption. Resveratrol-avobenzone structure-based hybrids (I-IV) present absorption maxima in the UVB range with slight differences between them, while resveratrol-OMC structure-based hybrids (V-VIII) showed main absorption in the UVA range. Among RESV-OMC hybrids, compounds V and VI exhibited higher UV absorption intensity, and compound VIII stood out for its broad-spectrum coverage in our simulations. Furthermore, both in silico and in vitro analyses revealed that compounds VII and VIII exhibited the highest antioxidant activity, with compound I emerging as the most reactive antioxidant within RESV-AVO hybrids. The study suggests a preference for the hydrogen atom transfer (HAT) mechanism over single-electron transfer followed by proton transfer (SET-PT) in the gas phase. With a strong focus on sustainability, this approach reduces costs and minimizes effluent production in synthesis research, promoting the eco-friendly development of new sunscreen active ingredients. The SPARTAN'20 program was utilized for the geometry optimization and energy calculations of all compounds. Conformer distribution analysis was performed using the Merck molecular force field 94 (MMFF94), and geometry optimization was carried out using the parametric method 6 (PM6) followed by density functional theory (DFT/B3LYP/6-31G(d)). The antioxidant behavior of the hybrid compounds (I-VIII) was determined using the highest occupied molecular orbital (εHOMO) and the lowest unoccupied molecular orbital (εLUMO) energies, as well as the bond dissociation enthalpy (BDE), ionization potential (IP), and proton dissociation enthalpy (PDE) values, all calculated at the same level of structural optimization. TD-DFT study is carried out to calculate the excitation energy using the B3LYP functional with the 6-31G(d) basis set. The calculated transitions were convoluted with a Gaussian profile using the Gabedit program.

Study of humic-like substances of dissolved organic matter using size exclusion chromatography and chemometrics

The study of dissolved organic matter (DOM) presents a significant challenge for environmental analyses and the monitoring of wastewater treatment plants (WWTPs). This is particularly true for the tracking of recalcitrant to biodegradation dissolved organic matter (rDOM) compounds, which is generated during the thermal pretreatment of sludge. This study aims to develop analytical and chemometric methods to differentiate melanoidins from humic acids (HAs), two components of rDOM that require monitoring at various stages of wastewater treatment processes due to their distinct biological effects. The developed method implements the separation of macromolecules through ultra-high-performance liquid chromatography size-exclusion chromatography (U-HPLC SEC) followed by online UV and fluorescence detection. UV detection was performed at 210, 254, and 280 nm, and fluorescence detection at six excitation/emission pairs: 230/355 nm, 270/355 nm, 240/440 nm, 270/500 nm, 330/425 nm, and 390/500 nm. Chromatograms obtained for each sample from these nine detection modes were integrated and separated into four molecular fractions: > 40 kDa, 20 - 40 kDa, 10 - 20 kDa, and < 10 kDa. To enhance analytical resolution and normalize the data, ratios were calculated from the areas of chromatographic peaks obtained for each detection mode. The results demonstrate the utility of these ratios in discriminating samples composed of HAs, melanoidins, and their mixtures, through principal component analysis (PCA). Low molecular weight fractions were found to be specific to melanoidins, while high molecular weight fractions were characteristic of HAs. For the detection modes specific to melanoidins, UV absorbance at 210, 254, and 280 nm were predominantly present in the numerators, with tryptophan-like fluorescence emissions in the denominators. Conversely, fluorescence emissions largely represented both numerators and denominators for HAs. This online method also enables the discrimination of pseudo-melanoidins, compounds revealing a nitrogen deficiency in their chemical structures.

Interaction mechanism of oseltamivir phosphate with bovine serum albumin: multispectroscopic and molecular docking study

Oseltamivir phosphate (OP) is an antiviral drug with potential risks to human health due to overuse, leading to serious consequences such as gastrointestinal disturbances, abnormal neuropsychiatric symptoms, and sudden death. Therefore, gaining an in-depth understanding of its interaction with proteins is crucial. We investigated the interaction between OP and bovine serum albumin (BSA) utilizing multispectral methods (i.e., fluorescence, ultraviolet absorption, circular dichroism) combined with molecular docking techniques. Fluorescence spectroscopy indicated that OP quenched BSA fluorescence by forming the OP-BSA complex. The Stern-Volmer constants (KSV) between OP and BSA were determined to be 3.06 × 103 L/mol, 2.36 × 103 L/mol, and 1.86 × 103 L/mol at 293 K, 298 K, and 303 K, respectively. OP occupies exclusively one binding site on BSA, and the fluorescent probe displacement measurements revealed that this is BSA site I. Thermodynamic data (∆H, ∆S, and ∆G) obtained by fitting the van’t Hoff equation were − 77.49 kJ/mol, -176.54 J/(mol∙K), and − 24.88 kJ/mol, respectively, suggesting that hydrogen bonding and van der Waals forces mainly participate in OP-BSA complex stabilization. Moreover, the reaction occurs spontaneously at room temperature. Synchronous fluorescence spectra indicated that OP interacts with tryptophan residue of BSA. The results of ultraviolet (UV) and 3D fluorescence spectroscopy indicated that the OP-BSA complex formation altered the microenvironment around amino acid residues. Circular dichroism spectra revealed that the addition of OP decreased the α-helix content of BSA by 7.13%. Docking analysis confirmed that OP binds to BSA site I through hydrogen bonding with amino acids VAL342, SER453, and ASP450. Finally, ADMET studies were conducted to explore the pharmacokinetics of OP as an antiviral drug.

Diagnosis of Bactericidal Components of Air-Plasma Jets by IR and UV Absorption Spectroscopy**

Diagnosis of Bactericidal Components of Air-Plasma Jets by IR and UV Absorption Spectroscopy**

Facile Lignin Extraction and Application as Natural UV Blockers in Cosmetic Formulations

Natural compounds are becoming increasingly popular in the fields of pharmaceuticals and cosmetics. One such compound is lignin, a plant-derived aromatic polymer that serves as a natural anti-ultraviolet agent. Conventional methods for extracting lignin from plant materials typically involve performing procedures in harsh environments, such as dissolving it in highly alkaline solutions or subjecting it to treatment in acidic conditions. In this study, lignin was extracted from coconut husk under milder conditions, using neutral solvents and ultrasonic treatment, which allowed us to obtain lignin with significantly improved properties. The developed method facilitated the creation of light-colored lignin, which was employed as a natural ingredient in sunblock cream. Furthermore, for the sake of comparison, lignin was extracted under more rigorous conditions using the traditional method. The research findings confirm that the light-colored lignin sample exhibits a higher level of UV absorption. Furthermore, light-colored lignin demonstrates a synergistic effect when combined with commercial moisturizing creams and sunscreens, leading to a significant enhancement in their SPF performance against both UVA and direct sunlight exposure. This study highlights the potential value of incorporating lignin as a valuable natural ingredient in sunblock and cosmetic products.

Full-spectrum cannabidiol reduces UVB damage through the inhibition of TGF-β1 and the NLRP3 inflammasome.

The thermodynamic characteristics, antioxidant potential, and photoprotective benefits of full-spectrum cannabidiol (FS-CBD) against UVB-induced cellular death were examined in this study. In silico analysis of CBD showed antioxidant capacity via proton donation and UV absorption at 209.09, 254.73, and 276.95 nm, according to the HAT and SPLET methodologies. FS-CBD protected against UVB-induced bacterial death for 30 min. FS-CBD protected against UVB-induced cell death by 42% (1.5 μg/mL) and 35% (3.5 μg/mL) in an invitro keratinocyte cell model. An invivo acute irradiated CD-1et/et mouse model (UVB-irradiated for 5 min) presented very low photoprotection when FS-CBD was applied cutaneously, as determined by histological analyses. Invivo skin samples showed that FS-CBD regulated inflammatory responses by inhibiting the inflammatory markers TGF-β1 and NLRP3. The docking analysis showed that the CBD molecule had a high affinity for TGF-β1 and NLRP3, indicating that protection against inflammation might be mediated by blocking these proinflammatory molecules. This result was corroborated by the docking interactions between CBD and TGF-β1 and NLRP3, which resulted in a high affinity and inhibition of both proteins The present work suggested a FS-CBD moderate photoprotective agent against UVB light-induced skin damage and that this effect is partially mediated by its anti-inflammatory activity.

π-Conjugated Structure Enhances the UV Absorption Performance of Carbon Dots and Application in the Design of Light-Colored Sunglasses

π-Conjugated Structure Enhances the UV Absorption Performance of Carbon Dots and Application in the Design of Light-Colored Sunglasses

Quantification of the Plasma Concentration of Vadadustat by High-Performance Liquid Chromatography with Ultraviolet Detection and Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry.

An inexpensive, simple, and accurate plasma concentration measurement system is needed to actively conduct pharmacokinetic and pharmacodynamic analyses of vadadustat, hypoxia-inducible factor-prolyl hydroxylase inhibitor, in clinical settings. In this study, the authors aimed to develop a method for measuring vadadustat in human plasma that could be applied for therapeutic drug monitoring using high-performance liquid chromatography with ultraviolet detection (HPLC-UV) in a clinical setting. Plasma samples (100 μL) were pretreated with acetonitrile using butyl paraoxybenzoate as an internal standard. Chromatographic separation was performed on a SunShell PFP C18 column (2.6 μm, 4.6 mm × 150 mm). The mobile phase consisted of (A) 20 mM of phosphate buffer (pH 2.4) and (B) acetonitrile (60:40, v/v), delivered isocratically at a flow rate of 1 mL/min. The analytes were detected by UV absorbance at a wavelength of 220 nm, and the column temperature was 40°C. To evaluate the applicability of HPLC-UV in a clinical setting, blood samples were collected at 19 time points from 7 patients who had been taking vadadustat. The calibration curve was linear over the concentration range of 0.2-150 mcg/mL (R2 > 0.99). Intra-assay and interassay accuracy, precision, and stability met the Food and Drug Administration recommendations. The vadadustat plasma concentrations of patients analyzed using the current HPLC-UV method were almost equal to those measured using ultra-performance liquid chromatography-tandem mass spectrometry (mean difference: 0.13 mcg/mL). Large variability in the dose-adjusted plasma concentrations of vadadustat at 12 hours after administration was observed between patients (coefficient of variation = 57.6%). This HPLC-UV method is a simple, accurate quantification method for evaluating plasma concentrations in patients taking vadadustat in a clinical setting.

Ultraviolet Photodissociation Dynamics of the 1-Methylallyl Radical.

The ultraviolet (UV) photodissociation dynamics of the 1-methylallyl (1-MA) radical were studied using the high-n Rydberg atom time-of-flight (HRTOF) technique in the wavelength region of 226-244 nm. The 1-MA radicals were produced by 193 nm photodissociation of the 3-chloro-1-butene and 1-chloro-2-butene precursor. The 1 + 1 REMPI spectrum of 1-MA agrees with the previous UV absorption spectrum in this wavelength region. Quantum chemistry calculations show that the UV absorption is mainly attributed to the 3pz Rydberg state (perpendicular to the allyl plane). The H atom photofragment yield (PFY) spectrum of 1-MA from 3-chloro-1-butene displays a broad peak around 230 nm, while that from 1-chloro-2-butene peaks at ∼236 nm. The translational energy distributions of the H atom loss product channel, P (ET)'s, show a bimodal distribution indicating two dissociation pathways in 1-MA. The major pathway is isotropic in product angular distribution with β ∼ 0 and has a low fraction of average translational energy in the total excess energy, ⟨fT⟩, in the range of 0.13-0.17; this pathway corresponds to unimolecular dissociation of 1-MA after internal conversion to form 1,3-butadiene + H. The minor pathway is anisotropic with β ∼ -0.23 and has a large ⟨fT⟩ of ∼0.62-0.72. This fast pathway suggests a direct dissociation of the methyl H atom on a repulsive excited state surface or the repulsive part of the ground state surface to form 1,3-butadiene + H. The fast/slow pathway branching ratio is in the range of 0.03-0.08.

Evaluation of the optical and magnetic properties of novel Nd0.9Zn0.1FeO3 perovskite nanoparticles and their adsorption of Pb2+ ions from water

Nd0.9Zn0.1FeO3 was prepared in a single-phase with an average crystallite size of 25.82 nm using a citrate combustion technique. The energy dispersive X-ray assures the chemical formula of the sample. The elemental mapping of Zn-doped NdFeO3 illustrates the good homogeneous distribution of the elements in the sample. Nd0.9Zn0.1FeO3 has antiferromagnetic properties with weak ferromagnetic components and has good UV absorbance. The values of the band gap for the direct and indirect transitions are 1.473 eV and 1.250 eV, respectively. The adsorption of nickel(II), cobalt(II), chrome(VI), cadmium(II), and lead(II) ions has been studied at pH 7. The highest removal efficiency (η = 73.72%) was observed for the lead ions from water. The current study has examined the kinetics, recoveries, and mechanisms of utilizing Nd0.90Zn0.10FeO3 to remove Pb2+ ions from water. The optimum conditions for the absorbing Pb2+ are pH 7 and a contact time of 60 min. The Freundlich isotherm model is the best model for the absorption of Pb2+ ions. While, the pseudo-second-order kinetic model describes the kinetic adsorption data. The sample has a good efficiency for removing Pb2+ ions from water several times.

The Impact of Lignin Biopolymer Sources, Isolation, and Size Reduction from the Macro- to Nanoscale on the Performances of Next-Generation Sunscreen

In recent years, concerns about the harmful effects of synthetic UV filters on the environment have highlighted the need for natural sun blockers. Lignin, the most abundant aromatic renewable biopolymer on Earth, is a promising candidate for next-generation sunscreen due to its inherent UV absorbance and its green, biodegradable, and biocompatible properties. Lignin’s limitations, such as its dark color and poor dispersity, can be overcome by reducing particle size to the nanoscale, enhancing UV protection and formulation. In this study, 100–200 nm lignin nanoparticles (LNPs) were prepared from various biomass by-products (hardwood, softwood, and herbaceous material) using an eco-friendly anti-solvent precipitation method. Pure lignin macroparticles (LMPs) were extracted from beech, spruce, and wheat straw using an ethanol–organosolv treatment and compared with sulfur-rich kraft lignin (KL). Sunscreen lotions made from these LMPs and LNPs at various concentrations demonstrated novel UV-shielding properties based on biomass source and particle size. The results showed that transitioning from the macro- to nanoscale increased the sun protection factor (SPF) by at least 2.5 times, with the best results improving the SPF from 7.5 to 42 for wheat straw LMPs and LNPs at 5 wt%. This study underscores lignin’s potential in developing high-quality green sunscreens, aligning with green chemistry principles.

Quantification of amino acids secreted by yeast cells by hydrophilic interaction liquid chromatography-tandem mass spectrometry.

Monitoring the levels of amino acids (AAs) in biological cell cultures provides key information to understand the regulation of cell growth and metabolism. Saccharomyces cerevisiae can naturally excrete AAs, making accurate detection and determination of amino acid levels within the cultivation medium pivotal for gaining insights into this still poorly known process. Given that most AAs lack ultraviolet (UV) chromophores or fluorophores necessary for UV and fluorescence detection, derivatization is commonly utilized to enhance amino acid detectability via UV absorption. Unfortunately, this can lead to drawbacks such as derivative instability, labor intensiveness, and poor reproducibility. Hence, this study aimed to develop an accurate and stable hydrophilic interaction liquid chromatography-tandem mass spectrometry analytical method for the separation of all 20 AAs within a short 17-min run time. The method provides satisfactory linearity and sensitivity for all analytes. The method has been validated for intra- and inter-day precision, accuracy, recovery, matrix effect, and stability. It has been successfully applied to quantify 20 AAs in samples of yeast cultivation medium. This endeavor seeks to enhance our comprehension of amino acid profiles in the context of cell growth and metabolism within yeast cultivation media.

Comparison of the effect of oxygen and nitrogen plasma treatments on the surface activation of PLA/rGO composites

Cold plasma is known as a method to enhance the adsorption of proteins on the surface of biomaterials. In this experimental study, the efficacy of oxygen and nitrogen plasma treatment on the activation of Poly L-lactic acid/reduced graphene oxide composite (PLAG) was investigated. For this purpose, the chemical, physicochemical, and morphological characteristics, ability to adsorb amino acid L-tyrosine, and biological behavior of the oxygen and nitrogen plasma-treated composites (PLAG-O and PLAG-N) were studied. Following the exposure to oxygen and nitrogen plasma, (PLAG-O) composites presented more enhancement in Raman C-C and C-H bonds. The evaluation of L-tyrosine adsorption revealed the higher intensity of FTIR C-N, C-C and N-H and Raman C-H chemical bonds and also lower intensity of L-tyrosine UV absorbance in solution medium for L-tyrosine-adsorbed oxygen plasma-treated (PLAG-Ot) compared to L-tyrosine-adsorbed nitrogen plasma-treated (PLAG-Nt) composites. More apparent L-tyrosine island-shaped zones were appeared all over the surface of PLAG-Ot composites through FE-SEM experiment. Moreover, conducting detailed AFM study revealed a higher difference in surface roughness (Ra) of the PLAG-O and PLAG-Ot (140 nm) compared to the PLAG-N and PLAG-Nt composites (25 nm). From the biological point of view, the oxygen plasma-treated composites presented better HDF cell behavior in terms of viability and attachment, as well. According to the results of this study, the oxygen plasma treatment exhibits a higher potential to activate Poly L-lactic acid–reduced graphene oxide composite surface compared to the surface treatment in nitrogen plasma.

Impact of incremental zinc-oxide incorporation on optical, magnetic, mechanical and photon transmission properties of K2O, SrF2, PbO containing borate-glasses

This study examines the radiation shielding properties of borate glass systems, with a focus on the simultaneous enhancement of optical, mechanical, and magnetic characteristics. The glass composition is represented by formula (55-x)B2O3+25PbO+10SrF2+10K2O + xZnO (where x: 0.0–10.0 mol%). By manipulating the ZnO concentration, we aimed to investigate its role as a radiation attenuator and its effects on the glass's optical, mechanical, and magnetic properties. Using traditional melt-quenching techniques, we produced the glass samples and examined their density, molar volume, linear attenuation coefficients (GLAC), mean free paths (GMFP), half-value layers (GHVL), and optical and magnetic properties. Our findings demonstrate that higher ZnO concentrations lead to a significant increase in density and a corresponding decrease in molar volume, thereby enhancing the glasses' ability to shield against gamma radiation. The radiation attenuation analysis revealed that increasing ZnO content substantially improves GLAC values across the energy range of 356–1333 keV. Additionally, ZnO incorporation decreases the optical bandgap, shifting the UV absorption edge to shorter wavelengths and enhancing UV dielectric capacity. Magnetic properties were assessed using vibrating sample magnetometer (VSM) measurements, showing a strong correlation between ZnO content and the effective atomic number (Zeff). It can be concluded that ZnO not only contributes to radiation shielding but also modifies the electronic structure of the glass, impacting its optical absorption properties.

Performance of Chitosan/Carbon Nanotube-Coated Ultrafiltration Membranes for Natural Organic Matter Removal from Drinking Water

The objective of this study is to improve the filtration efficiency of commercially available polyethersulfone (PES) ultrafiltration (UF) membranes, with a specific focus on removing natural organic matter (NOM) and preventing membrane fouling. The modification of UF membranes was accomplished by utilizing chitosan/multi-walled carbon nanotubes (CS/MWCNT-OH) and employing both dip and spin coating techniques. The membrane surface morphologies were evaluated using the Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and Energy-Dispersive X-ray Spectroscopy (EDX) techniques. Tests were carried out to assess the effectiveness of the membranes in a laboratory-scale system using two primary water sources from Istanbul, specifically the Melen River and Terkos Lake. Total organic carbon (TOC), UV254 absorbance, turbidity, and trihalomethane formation potential (THMFP) were all measured as part of a thorough analysis. The surface morphology investigations verified the effective deposition of MWCNT-OH nanoparticles onto the membrane surface. This was corroborated by the reduction in the water contact angle, showing an improvement in the hydrophilicity of the membrane. The modified membranes demonstrated much higher TOC removal rates compared to the original membranes. Specifically, the removal efficiencies for Melen River and Terkos Lake were 37.14% and 56.86%, respectively. Nevertheless, the alteration of the surface led to a decline in membrane flux as a result of the concurrent drop in pore size. To summarize, the results of this work highlights the considerable capability of surface modification using CS/MWCNT-OH to improve the performance and antifouling characteristics of commercial PES UF membranes.

Examining the dual effect of copper nanoparticles and nitrogen doping on Cu@N-TiO2

Abstract The study of six compositions of Cu@N-TiO2 with different amounts of copper and nitrogen synthesized using a sol–gel method is reported. X-ray diffraction patterns and Raman spectra indicated the formation of a single anatase TiO2 phase in all materials without evidence of secondary phases including copper or nitrogen. Electron microscopy images showed a homogeneous distribution of the copper particles around a TiO2 matrix, just as that the insertion of nitrogen did not have a significant effect on the morphology of the particles. X-ray photoelectron spectroscopy analysis confirmed that nitrogen was inserted in the atomic arrangement of titanium dioxide, while copper was presented mainly as metallic element on the TiO2 surface. Characterization of the optical properties and photoactivity test confirm that band gap strongly depends on the copper and nitrogen content phenomenon attributed to the combined presence of modifiers over the TiO2 surface and the promotion of a plasmonic effect, which displaced the absorption UV bands to higher wavelengths with respect to un-doped TiO2. The catalytic test performed using rhodamine-B as probe molecule, confirm that TiCuN2 and TiCuN3 samples exhibit the best decomposition percentages of 38 and 36 % respectively. Such results confirm the surface plasmon resonance effect associated to Cu particles on the TiO2 as main cause in the increase in current along synthesized samples and the use of cyclic voltammetry technique to identify these effects between 0.0 and 1.5 V.

Revisiting and Updating the Interaction between Human Serum Albumin and the Non-Steroidal Anti-Inflammatory Drugs Ketoprofen and Ketorolac

Ketoprofen (KTF) and ketorolac (KTL) are among the most primarily used non-steroidal anti-inflammatory drugs (NSAIDs) in humans to alleviate moderate pain and to treat inflammation. Their binding affinity with albumin (the main globular protein responsible for the biodistribution of drugs in the bloodstream) was previously determined by spectroscopy without considering some conventional pitfalls. Thus, the present work updates the biophysical characterization of the interactions of HSA:KTF and HSA:KTL by 1H saturation-transfer difference nuclear magnetic resonance (1H STD-NMR), ultraviolet (UV) absorption, circular dichroism (CD), steady-state, and time-resolved fluorescence spectroscopies combined with in silico calculations. The binding of HSA:NSAIDs is spontaneous, endothermic, and entropically driven, leading to a conformational rearrangement of HSA with a slight decrease in the α-helix content (7.1% to 7.6%). The predominance of the static quenching mechanism (ground-state association) was identified. Thus, both Stern–Volmer quenching constant (KSV) and binding constant (Kb) values enabled the determination of the binding affinity. In this sense, the KSV and Kb values were found in the order of 104 M−1 at human body temperature, indicating moderate binding affinity with differences in the range of 0.7- and 3.4-fold between KTF and KTL, which agree with the previously reported experimental pharmacokinetic profile. According to 1H STD-NMR data combined with in silico calculations, the aromatic groups in relation to the aliphatic moiety of the drugs interact preferentially with HSA into subdomain IIIA (site II) and are stabilized by interactions via hydrogen bonding and hydrophobic forces. In general, the data obtained in this study have been revised and updated in comparison to those previously reported by other authors who did not account for inner filter corrections, spectral backgrounds, or the identification of the primary mathematical approach for determining the binding affinity of HSA:KTF and HSA:KTL.

Newly plant-derived carbon in the deeper vadose zone of a sandy agricultural soil does not stimulate denitrification

Analysis of stable carbon (C) isotopic signatures (δ13C) in various soil C pools provides useful information on soil C sources, transport, and availability. Understanding the extent of deeper soil (below 40 cm) sequestration and transport of plant derived C is of particular interest as this provides a source for microorganisms to drive biological denitrification (as indicated by denitrification enzyme activity, DEA) and hence mitigate the nitrate leaching to groundwater. Meanwhile, studies on deeper soil C sequestration are rare due to methodological constraints. This study was done in deeper vadose zone (0–160 cm) of a sandy agricultural soil in a humid and temperature zone after a C3-C4 vegetation change taking advantage of the marked isotopic differences between C3 and C4 plants. It took place in a site previously grown with C3 crops (beet, barley, grass), but where C4 crops (maize) were grown continuously for the last 20 years. The other site where C3 crops were continuously grown was used for comparison. Specifically, the δ13C signature in top and deeper soil layers was used to distinguish between old C3– and newly C4-plant derived C in four C pools, i.e., bulk soil C, hot- and cold-water extractable C, and respired CO2-C. The δ13C signature between C3 soils and C3-C4 shifted soils was similar for bulk soil C but significantly different for water extractable and respired C pools. Hence, we estimated that the contribution of newly derived C to bulk soil C was negligible, whereas the contributions to the other C pools amounted up to 28.4 % along the soil profile. This emphasizes the importance of simultaneously analysing δ13C signature in various soil C pools to accurately assess C vertical transport and distribution. The concentrations of cold-DOC and values of specific ultraviolet visible absorbance of the wavelengths 254 and 280 nm decreased from 50 to 130 cm soil depths, while they increased below these depths. However, this suggested rise in C chemical quality at the deepest soil depths did not cause an increase in soil respiration activity or DEA, which was attributed to the protective effects of iron and aluminium oxides on C decomposition. Upon the application of labile C and N substrates, the deepest soil layers displayed a significantly increased DEA, suggesting the presence of a relatively abundant population of active denitrifying organisms. Overall, this study documents the presence of plant-derived C in the deeper vadose zone. Meanwhile, this particular C pool might not be an important substrate to drive deep-soil denitrification due to constraints imposed by the protection by metal oxides.