Absorption Spectroscopy Techniques Research Articles

Direct and Indirect Effects of Land Use on Dissolved Organic Matter in a Typical Karst River

Land use can directly affect the abundance of riverine dissolved organic matter (DOM) by transporting terrestrial organic matter to rivers and can also indirectly enhance local production of DOM by increasing riverine nutrient loading. This study investigated the characteristics and spatial distribution of DOM components in the Furong River during the rainy season (July) using ultraviolet-visible light absorption spectroscopy (UV-VIS) and three-dimensional excitation emission matrix fluorescence spectroscopy-parallel factor analysis (EEM-PARAFAC) techniques. Furthermore, correlation analysis and the partial least squares path model (PLS-PM) were used to identify and quantify the direct and indirect impacts of land use on DOM at multiple scales. The results revealed that:① the direct effects of land use on DOM were generally stronger than the indirect effects. ② The responses of different DOM components to riverine nutrient status and land use varied, with dissolved organic carbon (DOC) and colored dissolved organic matter (CDOM) components being more susceptible to riverine nutrient status and fluorescent dissolved organic matter (FDOM) being more sensitive to land use. ③ The direct impact intensity of land use on DOC and CDOM fluctuated slightly with the spatial scale, but the total impact intensity had no visible spatial scale difference, and the direct impact intensity on the FDOM component decreased with the increase in spatial scale. ④ Dryland, urban and other construction land, patch density (PD), edge density (ED), and Shannon's diversity index (SHDI) were typical land use metrics that exacerbated DOM abundance, whereas paddy field, shrubland, largest patch index (LPI), and aggregation index (AI) were typical land use metrics that effectively mitigated DOM abundance. Total nitrogen (TN), nitrate nitrogen (NO3--N), and dissolved total phosphorus (DTP) were water quality parameters that were significantly affected by land use and were closely related to DOM components, that is, nitrogen and phosphorus played an important "intermediary" role in "land use-riverine DOM." FDOM could be used as indicators to measure the strength of terrestrial organic matter directly input to rivers by land use.

The Influence of the Lactation Period and the Type of Milk on the Content of Amino Acids and Minerals in Human Milk and Infant Formulas.

(1) Background: This study investigated the effect of the lactation period and the type of infant formula on the content of amino acids and selected minerals in an infant's food; (2) Methods: The study material consisted of breast milk (colostrum, n = 38; transitional milk, mature milk, n = 38) and three types of infant formulas (for first and follow-on feeding). Amino acid content was determined using an automatic amino acid analyzer, while minerals were determined by the atomic absorption spectrometry (AAS) technique; (3) Results: Breast milk and infant formulas contained a full range of essential amino acids. In most cases, the content of individual amino acids and minerals decreased with increasing lactation. In infant formulas, there were higher contents of phenylalanine, glutamic acid, proline, serine, and tyrosine in follow-on milk (p < 0.05). The EAA/TAA ratio in breast milk and infant formulas was similar, but the milk differed in their qualitative composition. Infant formulas contained levels of individual minerals that were several times higher-especially Mg, Ca, Mn, and Fe.; (4) Conclusions: Colostrum is more concentrated, and the level of amino acids and minerals is higher in it; as the milk matures, it decreases. In most cases, the content of individual amino acids and minerals is higher in infant formulas than in human milk, which is established through strict Codex Alimentarius procedures to ensure the proper development of infants.

Elemental analysis of Fadogia ancylantha leaves used as a nutraceutical in Mashonaland West Province, Zimbabwe.

In this study, the concentrations of the essential elements to the human body N, K, Mg, P, Ca, Fe, Mn, and Zn of the fermented and non-fermented Fadogia ancylantha leaf samples were analysed to assess their nutritional value in two different areas in Zimbabwe: Mhangura (Mashonaland West, Province) and Alaska (Mashonaland West Province). Atomic absorption spectroscopy and ultraviolet spectrophotometry techniques were used to measure the concentrations of the minerals. The concentrations of manganese were significantly high (p < 0.05) in non-fermented treatments, with Mhangura samples having 0.447 mg/g and Alaska samples having 0.453 mg/g. Iron was high in fermented samples with Mhangura samples having 0.245 mg/g and Alaska samples having 0.270 mg/g. The concentrations of manganese and iron in Fadogia ancylantha can be used to supplement the recommended daily doses in pregnant, menstruating, and lactating women. The study, therefore, recommends that Fadogia ancylantha be used as a nutraceutical for the supplementation of iron and manganese.

Comparative Assessment of Heavy Metal Concentration in Some Edible Spinach (Amaranthus hybridus) in Southern Taraba (Ibi, Wukari and Donga), Nigeria

This study focuses on the assessment and comparative concentrations of some heavy metals in spinach (Amaranthus hybridus), cultivated in Wukari, Ibi, Donga local government area of Taraba State in Nigeria. The research is motivated by the indiscriminate use of bulk chemicals for farming activities in the communities under review. The study employed random sampling techniques in collecting the samples of the spinach. The edible part were digested and analyzed for the following heavy metal content: Lead, Zinc, Copper, Nickel, Iron, Cobalt, Chromium, Manganese, and Cadmium. The Atomic Absorption Spectroscopy (AAS) technique was used to analyze the samples. The results for the main concentration of heavy metal were revealed. The concentration of heavy metals in the spinach obtained from the three different samples varies. It was observed that, the sample obtained from Wukari has the highest accumulation of heavy metals. The concentrations of Pb, Mn and Cr were found to be higher than the permissible limits in Wukari spinach. Cd was not detected in the three (Ibi, Donga and Wukari). Pb was not detected in Ibi and Donga. Cu and Ni were not detected in Donga. Based on the findings from this study, spinach from Ibi and Donga are recommended for consumption compared to Wukari, since most of the heavy metals in this study areas are within the standard permissible limit set by WHO/FAO. Similarly, the daily intake of heavy metal (DIM) and the health risk index (HRI) analysis from the 3 study areas also falls within the acceptable permissible level. Farmers and consumers should be adviced appropriately on the health implications of excessive heavy metal consumption in vegetables.

Origin of Enhancement of Orbital Magnetic Moment in SiO2-Coated Fe3O4 Nanocomposites Studied by X-ray Magnetic Circular Dichroism.

In this study, magnetic Fe3O4 nanoparticles (NPs) were dispersed uniformly by varying the thickness of the SiO2 coating, and their electronic and magnetic properties were investigated. X-ray diffraction confirmed the structural configuration of monophase inverse-spinel Fe3O4 NPs in nanometer size. Scanning electron microscopy revealed the formation of proper nonporous crystallite particles with a clear core-shell structure with silica on the surface of Fe3O4 NPs. The absorption mechanism studied through the zeta potential indicates that SiO2-coated Fe3O4 nanocomposites (SiO2@Fe3O4 NCs) possess electrostatic interactions to control their agglomeration in stabilizing suspensions by providing a protective shield of amorphous SiO2 on the oxide surface. High-resolution transmission electron microscopy images demonstrate a spherical morphology having an average grain diameter of ∼11-17 nm with increasing thickness of SiO2 coating with the addition of a quantitative presence and proportion of elements determined through elemental mapping and electron energy loss spectroscopy studies. Synchrotron-based element-specific soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) techniques have been involved in the bulk-sensitive total fluorescence yield mode to understand the origin of magnetization in SiO2@Fe3O4 NCs. The magnetization hysteresis of Fe3O4 was determined by XMCD. At room temperature, the magnetic coercivity (Hc) is as high as 1 T, which is about 2 times more than the value of the thin film and about 5 times more pronounced than that of NPs. For noninteracting single-domain NPs with the Hc spread from 1 to 3 T, the Stoner-Wohlfarth model provided an intriguing explanation for the hysteresis curve. These curves determine the different components of Fe oxides present in the samples that derive the remnant magnetization involved in each oxidation state of Fe and clarify which Fe component is responsible for the resultant magnetism and magnetocrystalline anisotropy based on noninteracting single-domain particles.

Different shape-controlled synthesis and catalytic property studies on bismuth nanomaterials

Bi with four different morphologies (zero-dimensional (0D) nanoparticles, one-dimensional (1D) nanowires, two-dimensional (2D) nanoplates, and three-dimensional (3D) shuttle like structures) was successfully synthesized by changing the synthetic conditions. The Bi nanostructures were characterized in terms of structure, morphology, surface characteristics, optical properties and catalytic activity using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), photoluminescence (PL), UV–vis absorption spectroscopy (UV–Vis) and total organic carbon (TOC) analyzer techniques, respectively. The PL spectra is shown that the reduction of the size of Bi nanomaterials can reduce the recombination rate of photoelectrons and holes, which leads to the effective separation of photocharge carriers and the lowest photoelectron and hole recombination rates. The band gap values of Bi nanoparticles, nanowires, nanoplates and shuttle like structures are 2.71 eV, 2.76 eV, 2.92 eV and 3.22 eV respectively, favouring the harvesting of visible-light. The experimental results of the degradation performance of Bi with different morphologies exhibited that 99.9%, 97.9%, 96.2% and 74.4% degradations of the Rhodamine B (Rh B) was observed for Bi nanoparticles, nanowires, nanoplates and shuttle like structures, respectively. During the degradation of RhB, with the prolongation of treatment time to 90 min, the highest removal rates of chemical oxygen demand (COD) and TOC was 73.5% and 68.4%, respectively. According to TOC analysis, more than 68% of the carbon in the dyes will produce CO2 products. The removal efficiency is attributed to the production of ·O2−, ·OH and h+ and their mineralization to RhB. At the same time, the achieved results also reveal that Bi2O3 and BiOCl was found in Bi surfaces before and after catalytic degradation, which was confirmed by XPS and FTIR technology. In addition, Bi with the same morphology performed different catalytic activities in Rh B solution with different pH values. It was found that the degradation efficiency increased evidently when the pH value decreased. The mechanism of Bi photocatalytic activity was proposed based on the results of product analysis, radical capture and XPS analysis.

Atomically dispersed copper-nickel electrocatalyst for highly selective electroreduction of CO2 at a wide potential range

Designing and synthesising electrocatalysts with low overpotential, high activity, selectivity, and stability for the CO2 reduction reaction (CO2RR) is crucial for addressing environmental challenges and realising the artificial carbon cycle. In this study, we successfully synthesised a nitrogen-doped carbon-supported diatomic electrocatalyst comprising atomically dispersed CuN4 and NiN4 bimetallic centers. This was confirmed through extensive characterisation using high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy techniques. The as-synthesised CBN-CuNi electrocatalyst exhibited exceptional selectivity and stability in CO2RR. Over a wide potential range from − 0.60 to − 1.10 V vs RHE, CBN-CuNi maintained over 90% Faraday efficiency for CO (FECO) production. Notably, at − 0.9 V vs RHE, it achieved a remarkable selectivity with a maximum FECO of 97.9%, surpassing single metal catalysts, including CBN-Ni and CBN-Cu. Furthermore, CBN-CuNi demonstrated outstanding stability, sustaining over 90% FECO production for 40 h of continuous electrolysis, surpassing many existing electrocatalysts. These findings highlight the potential of the as-synthesised bimetallic electrocatalyst CBN-CuNi in the electrochemical reduction of CO2 to CO, contributing to advancing the artificial carbon cycle and addressing environmental concerns.

A reaction-based carbazole-dicyanovinyl conjugated colorimetric and ratiometric fluorescent probe for selective detection of cyanide ions

In the present work, 4-(9′-hexylcarbazol-3′-yl)benzylidenemalononitrile 5 (probe L) was tested as a colorimetric and ratiometric fluorescent probe in dimethyl sulfoxide (DMSO) medium towards anions, cations and neutral molecules. The sensing properties of probe L were investigated by using UV–Vis absorption and fluorescence spectroscopy techniques. Probe L showed selectivity and sensitivity towards cyanide ions (CN–) in the presence of analytes used. Upon the addition of CN–, intramolecular charge transfer (ICT) band at 425 nm in UV spectrum disappeared. In addition, ICT emission intensity at 593 nm decreased and ligand-centred (LC) emission intensity at 480 nm increased. These findings indicate that nucleophilic conjugate addition of CN– to the dicyanovinyl group of probe L successfully occurs, hence forming a new adduct between probe L and CN–. In this adduct, π-conjugation was partially blocked, and the ICT transfer was hindered. Adduct formation was proved by Job’s plot, 1H NMR and FT-IR analysis. Probe L showed very low limit of detection (LOD) value of 1.467 nM towards CN–. Probe L was also applied to the CN– detection in real-world water samples by the spike and recovery method. The maximum relative standard deviation (RSD) value was 4.24, indicating this method works successfully. Therefore, probe L could find a potential use in detection of CN– in liquid media.

X-ray absorption fine structure (XAFS)-based radionuclide research at the KIT Light Source

Abstract. In the past two decades, X-ray absorption spectroscopy (XAS) and related synchrotron-based radionuclide speciation techniques have become indispensable, supporting open issues in fundamental radiochemistry and nuclear waste disposal alike. Physicochemical structure information – encoded in the element-specific X-ray absorption fine structure (XAFS) – is obtained by the precise determination of the linear mass absorption coefficient μ(E) of a specimen in an X-ray energy window ΔE encompassing an electronic bonding level of a selected atom type. The characteristic modulations of μ(E) in the vicinity of an “absorption edge” (i.e., the steeply rising absorption probability of photons tuned to the binding energy of inner shell “core” electrons) are attributed to electronic transitions into unoccupied states due to the photoelectric effect. While absorption features close to the edge (arising from excitations into molecular orbitals or empty band structure levels close to the Fermi level) are generally denoted as an X-ray absorption near-edge structure (XANES), the scattering states at higher excitation energies are causing the well-known extended X-ray absorption fine structure (EXAFS). EXAFS oscillations of the post-edge μ(E) are caused by the periodicity of the constructive and destructive interference of outbound and backscattered inbound photoelectron waves (superimposing at the absorbing atom site) when continuously increasing the excitation energy. Quantitative analysis of EXAFS data based on electron scattering theory is a well-established short-range structural probe, providing precise values of interatomic distances (between the absorber atom and its neighbors) and additional information on the type, number, and ordering of neighbor atoms within a local cluster. Recent significant advancements in the quantum theoretical description of core-excited final states have been successful in overcoming persisting ambiguities in XANES data interpretation. Meanwhile, although there are more than 50 synchrotron radiation centers operational in the world, facilities with specialized beamline infrastructure and safety protocols to allow experiments on radioactive samples with activities beyond the exemption limits are still scarce. At the KIT Light Source (at the Karlsruhe Institute of Technology, Karlsruhe, Germany), the Institute for Nuclear Waste Disposal (Institut für Nukleare Entsorgung, INE) operates two beamline end-stations dedicated to the investigation of radionuclide materials by XAFS spectroscopy and related techniques, i.e., the INE-Beamline (operational since 2005) and the ACT station of the CAT-ACT (CATalysis and ACTinide) wiggler beamline (operational since 2016). Samples with total activities amounting to 1.0×106 times the isotope specific exemption limits and 200 mg of fissile isotopes 235U and 239Pu are feasible at both beamlines. Highly versatile detection systems and sample holders – generally avoiding extensive shielding or sample handling in a glove box – have been conceived since the initial commissioning of the beamlines and have enabled unique XAFS measurements such as the first ever investigation of aqueous technetium species at the Tc L3 edge. Investigations of highly radioactive specimens (e.g., spent nuclear fuel or nuclear waste glass fragments) are feasible, regardless of the actual contact dose rate if the radiation field is limited to a few microsieverts per hour at the edge of the experimental table.

Low-Temperature Cavity-Enhanced Spectroscopy with a Diode Laser: Vibration–Rotation Absorption of CO (3ν) at 80 K and CH3C≡C–H (2ν1) at 165 K

A rotational resolution cavity-enhanced absorption spectroscopy (CEAS) technique is presented for infrared (IR) absorption studies at temperatures between 77 and 300 K. The cavity consists of an aluminum tube with two highly reflecting near-IR mirrors at each end. The cavity is attached to the cold head of a liquid nitrogen cryostat inside a vacuum chamber. In this way, all the cavity components are the temperature of the cold head. The spectra are obtained with a tunable diode laser and lock-in detection. The laser is modulated with an electro-optic modulator and coupled to the optical cavity. To illustrate the use of the technique, the vibrational–rotational overtone transitions (υ = 0→3) of carbon monoxide at 295 and 80 K and the acetylenic C–H (υ = 0→2) bond of CH3C≡C–H at 293 and 165 K are obtained. Temperatures are obtained with a Boltzmann distribution calculation that involves rotational intensities and energies from the spectra. Spectroscopic constants agree with previous determinations using other methods. An average of signals over the entire range of the absorption produces a rotational intensity distribution with some deviations. The calculated temperature based on the Boltzmann distribution is in very good agreement with the temperature measured with a silicon temperature sensor attached to the cell. Comparison with other experimental approaches to CEAS and the importance of the technique for applications in astrochemistry are discussed.

Plasmonic nanobipyramids with photo-enhanced catalytic activity under near-infrared II window for effective treatment of breast cancer

Nanozyme-based catalytic therapy is an effective method for cancer treatment, but insufficient catalytic activity presents a challenge in achieving optimal therapeutic outcomes. External light can provide an innovative approach to modulate nanozyme catalytic activity. Herein, we report on plasmonic gold nanobipyramid@cuprous oxide (Au NBP@Cu2O) nanozyme for the effective phototherapy of breast cancer. In the tumor microenvironment, Cu+-mediated Fenton-like reaction catalyzes the generation of toxic hydroxyl radicals (•OH) from endogenous hydrogen peroxide to induce apoptosis. Additionally, the Au NBP@Cu2O nanostructure improves the absorption performance of Au NBPs in the near-infrared II region through near-field enhancement of equipartite exciters and achieves a high photothermal conversion efficiency value of 58%. Remarkably, the Au NBP@Cu2O nanoheterostructure can capture hot electrons induced by equipartition excitations and promote electron-hole separation under 1064 nm laser irradiation, facilitating the production of more reactive oxygen species (ROS). The mechanism behind this enhanced catalytic activity was unraveled using femtosecond transient absorption spectroscopy. Both in vitro and in vivo investigations have demonstrated the efficacious tumor therapeutic potential of Au NBP@Cu2O nanozyme, particularly under 1064 nm laser irradiation. Furthermore, the proposed therapeutic approach has been proved to effectively block tumor metastasis, providing a promising strategy for the development of multifunctional nanotherapeutics to tackle metastatic tumors. Statement of significanceA highly effective plasmonic nanozyme has been developed to improve catalytic therapy for breast cancer. When exposed to 1064 nm laser irradiation, Au NBP@Cu2O nanozyme can promote the separation of hot electrons and holes thereby facilitating the production of reactive oxygen species. Hot electrons transfer behavior is unveiled by femtosecond transient absorption spectroscopy technique. This enhanced catalytic activity, along with the intrinsic photothermal effect, effectively kills tumor cells.

Temperature determination of multiple gas slabs using a single absorption line

In this study, temperatures of multiple gas slabs are measured from a single absorption line using a tunable diode laser absorption spectroscopy technique. While typical laser absorption spectroscopy techniques require two or more absorption lines to determine the gas temperatures, however, this study presents the temperature determination method using an absorption line and its conditions for successful application. To generate two air slabs along with a single laser path, a gas heating apparatus composed of two chambers is used. The air is used as a test gas and a tunable diode laser absorption spectroscopy system is set up to detect an absorption line of the oxygen molecule in the air. Using the spectroscopic characteristics that the line shape and absorption strength are functions of gas properties and beam path length, temperature values of multiple gas slabs are experimentally determined by matching a measured spectral absorbance with a calculated one with known pressure and beam path length values. The determined temperatures are compared with temperature values set using thermocouples. It is observed that the temperatures of the gas slabs can be successfully measured when the pressures of the gas slabs are considerably different. The effect of gas properties and beam path length on the temperature determination is discussed. Measurement uncertainty due to random noise in the signal is investigated through a simulation approach.

A Reversible Fluorescent Chemosensor for the Selective Detection of Cu2+ and CN- ions by Displacement Approach.

A novel fluorescence chemosensor BDP (2-(1-(benzothiazol-2-yl)-5-(4-(diphenylamino)phenyl)-4,5-dihydro-1H-pyrazol-3-yl)phenol) has been synthesized and its sensing behavior has been screened towards various cations by absorption, emission and mass spectroscopic techniques. The probe BDP detects Cu2+ ions preferentially over other metal ions, and the resulting BDP-Cu2+ ensemble acts as a secondary sensor for cyanide anion detection over other anions. The fluorescence intensity of the probe BDP is quenched when it comes into contact with Cu2+ ions, but it is increased reversibly when it comes into contact with cyanide anion, according to spectroscopic measurements. Along with this, optical studies indicate that the sensor BDP has capability to sense Cu2+and CN- ions selectively over other examined competitive ions with the LOD of 2.57×10-8 Mand 2.98×10-8 M respectively. The detection limit of Cu2+ions is lower than the WHO recommended Cu2+ions concentration (31.5 µM) in drinking water. On the basis of "on-off-on" fluorescence change of the probe BDP upon interaction with Cu2+ and CN- ions, a possible mechanism for this selective sensing behavior was presented and IMPLICATION logic gate was successfully designed. Furthermore, cell imaging investigations were used to investigate the probe BDP's biological applicability.

Highly Efficient HTM-Free Tin Perovskite Solar Cells with Outstanding Stability Exceeding 10000 h.

The bottleneck in the rapid development of tin-based perovskite solar cells (TPSCs) is the inherent chemical instability. Although this is being addressed continuously, the device performance has not improved further due to the use of PEDOT:PSS as the hole-transport material (HTM), which has poor long-term stability. Herein we have applied commercial ITO nanoparticles over ITO glass substrates and altered the surface chemistry of the ITO electrode via a simple two-step thermal annealing, followed by a UV-ozone treatment. These surface-modified ITO electrodes display promising interfacial characteristics, such as a suitable band alignment owing to significantly reduced surface carbon contamination, increased In-O bonding, and reduced oxygen vacancies, that enabled fabrication of an HTM-free TPSC device according to a two-step method. The fabricated device possessed an outstanding power conversion efficiency (PCE) of 9.7%, along with a superior long-term stability by retaining over 90% of the initial PCE upon shelf storage in a glovebox for a period of over 10000 h. The application of ITO nanoparticles led to effective interfacial passivation, whose impacts on the long-term durability were assessed using electrochemical impedance spectroscopy, time-resolved photoluminescence decay profiles, and femtosecond transient absorption spectroscopy techniques.

New Design Valve in Flow Injection System for the Determination of Pb(II) in Biological and Environmental Samples

A strategy to design an injection valve for a streamlined flow injection technique is described as speed and low-cost materials available in the environment for the determination of Pb(II) ion using the organic reagent 4-((4-methoxyphenyl)diazenyl)benzene-1,3-diol at a wavelength of 498 nm. The scope of the study is to find the optimal conditions, including the flow rate of the carrier, the dispersion coefficient, the length of the reaction coil, and the calibration drawing. The results showed that the optimum length of the reaction coil is 20 cm, and the optimum flow rate is 9.1 mL/min, which is equivalent to the pumping rate of 70 F/min. The range of linearity of the study was revealed by a calibration curve of 0.5–27 mg/L, slope = 1.507, correlation coefficient = 0.9995, the limit of quantitative (LOQ) = 0.088 mg/L, and limit of detection (LOD) = 0.026 mg/L. The system under study has a characteristic efficiency. The dispersion coefficient was calculated for concentrations of 10–15 mg/L Pb(II) ion. Furthermore, the accuracy of the flow injection technique in the estimation process was studied and compared with the Flame Atomic Absorption Spectroscopy (FAAS) technique.

Mitigating the Trade-Off between Non-Radiative Recombination and Charge Transport to Enable Efficient Ternary Organic Solar Cells.

Ternary organic solar cells (OSCs) have attracted intensive studies due to their promising potential for attaining high-performing photovoltaics, whereas there has been an opening challenge in minimizing the open circuit voltage (Voc) loss while retaining the optimal carrier extraction in the multiple mixture absorbers. Here, we systemically investigate a ternary absorber comprised of two acceptors and a donor, in which the resultant Voc and fill factor are varied and determined by the ratios of acceptor components as a result of the unbalance of non-radiative recombination rates and charge transport. The transient absorption spectroscopy and electroluminescence techniques verify two distinguishable charge-transfer (CT) states in the ternary absorber, and the mismatch of non-radiative recombination rates of those two CT states is demonstrated to be associated with the Voc deficit, whilst the high-emissive acceptor molecule delivers inferior electron mobility, resulting in poor charge transport and a subpar fill factor. These findings enable us to optimize the mixture configuration for attaining the maximal-performing devices. Our results not only provide insight into maximizing the photovoltage of organic solar cells but can also motivate researchers to further unravel the photophysical mechanisms underlying the intermolecular electronic states of organic semiconductors.

Green Synthesis and Bioactivity of Aliphatic N-Substituted Glycine Derivatives.

Standard amino acids have an asymmetric α-carbon atom to which -COOH, -NH2, -H, and -R groups are bonded. Among them, glycine is the simplest (R = -H) with no asymmetric carbon, and other natural amino acids are C-substituted of glycine. Here, we have designed and made a green synthesis of some new N-substituted glycine derivatives with R-(NH)CH2-COOH formula, where R is flexible and hydrophobic with different chain lengths and benches of the type propyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-aminoheptyl, and octyl. These glycine derivatives were characterized by recording their melting points and FT-IR, mass, 1H NMR, and 13C NMR spectra. DFT studies revealed that 2-aminoheptyl glycine had the highest electronegativity value and can thus act as a good bidentate ligand for the metal centers. ADME comparative results and bioavailability radars indicated that both octyl- and 2-aminoheptyl glycine had the most lipophilicity, making them good agents in cell passing. Furthermore, lipophilicity determination showed that octyl glycine was the best and propylgly was more soluble than others. Based on solubility, lipophilicity, and dipole moment values, propyl- and 2-aminoheptyl-glycine were considered for bio-macromolecular interaction studies. Thus, the interaction of these two agents with DNA and HSA was studied using absorption spectroscopy and circular dichroism techniques. Due to the presence of the R-amine group, they can interact with the DNA by H-binding and hydrophobicity, while electrostatic mode could not be ruled out. Meanwhile, molecular docking studies revealed that octyl- and 2-aminoheptyl glycine had the highest negative docking energy, which reflects their higher tendency to interact with DNA. The DNA binding affinity of two candidate AAs was determined by viscosity measurement and fluorescence emission recording, which confirms that groove binding occurs. Also, the toxicity of these synthesized amino acid derivates was tested against the human foreskin fibroblast (HFF) cell line. They showed IC50 values within the range of 127-344 μM after 48 h with the highest toxicity for 2-aminoheptyl glycine.

Exploring the pH-Responsive Interaction of β-Blocker Drug Propranolol with Biomimetic Micellar Media: Fluorescence and Electronic Absorption Studies.

Interaction of neutral and charged lipophilic beta-blocker drug, propranolol (PPL) with biomimicking nanocavities formed by micelles bearing same and opposite charges namely, cationic cetyltrimethylammonium bromide (CTAB), a surface-active ionic liquid 1-hexadecyl-3-methylimidazolium chloride (HDMIC) and anionic sodium dodecyl sulphate (SDS) have been investigated using fluorescence and absorption spectroscopic techniques. Binding of PPL to SDS at pH < pKa is characterised by biphasic interactions with decrease in fluorescence intensity at lower concentrations and subsequent increase post micellization. All the surfactants show significant interactions with the neutral drug molecule at pH > pKa, which is evident from the strongest binding constant ( ) values at pH 10.4. Results of quenching studies indicate that the location of drug molecule is determined by its charge, which is influenced by both pH and charge on micelle surface. For PPL-CTAB and PPL-HDMIC systems, quenching was strongest at pH 10.4, moderate at pH 7.4 and was absent at pH 3.5. However, the PPL-SDS system displayed similar values at all pH conditions, suggesting that the probe is at the same position regardless of pH. Non-covalent interactions, which play crucial role in biological systems, are similarly the primary driving force governing the interaction between PPL and surfactant micelles.

Thiocyanato and Schiff base coordinated mono/di-nuclear Ni(II) complexes: Syntheses, crystal structures and protein binding

Two Ni(II) complexes, [Ni2(L1)2(SCN)2(dmf)2] (1) and [Ni(L2)(SCN)] (2) [where HL1 = 2-ethoxy-6-[(2-phenylamino-ethylimino)-methyl]-phenol, HL2 = 2-[(2-pyrrolidin-1-yl-ethylimino)-methyl]-phenol, dmf = N,N-dimethylformamide], have been synthesized and characterized by single crystal X-ray diffraction, IR and mass spectroscopic studies. In the centrosymmetric complex 1, two Ni(L1) fragments are connected via µ2-oxo bridges and the metals complete the octahedral coordination with one thiocyanate and one dmf solvent molecule. In complex 2, the Ni(II) ion is coordinated by the tridentate Schiff base and a thiocyanate in a square planar environment. Both the complexes form 1D supra-molecular network through CH…π interactions and complex 2 also via H-bonding. The interaction of complexes with serum albumins was investigated using UV–Vis absorption and fluorescence spectroscopic techniques.

A mid‐infrared laser absorption sensor for calibration‐free measurement of nitric oxide in laminar premixed methane/ammonia cofired flames

AbstractAn interband cascade laser (ICL)‐based absorption sensor was developed for calibration‐free and high‐fidelity measurement of nitric oxide (NO) in laminar premixed methane/ammonia cofired flames using a combination of a micro‐probe and a low‐pressure, high‐temperature gas cell. The developed sensor, which has been shown to be particularly suitable for kinetic studies of ammonia combustion, used a tunable, continuous, narrow‐linewidth, free‐space ICL operating at ~5.2 μm to target the optimal NO transition centered at 1900.07 cm−1. A direct absorption spectroscopy technique with a reduced line model was implemented for calibration‐free measurements. Comprehensive experiments were first conducted to evaluate the sensor performance against the standard gas mixture at varied pressure from 20 to 101 kPa at 393 K, showing a relative difference of ≤2.5% and a measurement uncertainty of ≤2.0%. Such a sensor shows a minimum detection limit of ~2 ppm at the integration time of 1 s. The sensor was then applied for investigating the NO formation in ammonia‐methane cofiring flames with various ammonia blending ratios; the acquired experimental data was further used as benchmark data for evaluation of literature chemical mechanisms for ammonia combustion. The developed sensor system was demonstrated to be capable of providing quantitative and spatially resolved measurement of NO in ammonia‐methane cofired flames.