A bidentate (N- and O-) imine-based ligand (L 1 ) and its metal complexes of types [CuII(L 1 ) 2 ] (C 1 ) , [CuII(L 1 )(Phen)] (C 2 ) , [CoIII(L 1 ) 2 ] (C 3 ) , and [CoIII(L 1 )(Phen)] (C 4 ) (L 1 = 2-((E)-(6-fluorobenzo[d]thiazol-2-ylimino)methyl)-4-chlorophenol and phen = 1,10-phenanthroline) were synthesized as potential chemotherapeutic drug candidates. The prepared complexes were structurally characterized by spectral techniques (NMR, FT-IR, LC-MS, EPR, and electronic absorption), thermogravimetric analysis (TGA/DTA), magnetic moment, and CHNO elemental analysis. Spectroscopic studies suggested the distorted octahedral structure for all complexes. In vitro bioassay studies include binding and nuclease activities of the ligand and its complexes with target calf thymus- (CT-) DNA were carried out by employing UV-Vis, fluorescence spectroscopy, viscosity, and gel electrophoresis techniques. The extent of binding propensity was determined quantitatively by Kb and Ksv values which revealed a higher binding affinity for C 2 and C 4 as compared to C 1 and C 3 . In addition, the scavenging superoxide anion free radical (O∙-2) activity of metal complexes was determined by nitroblue tetrazolium (NBT) light reduction assay. Molecular docking studies with DNA and SOD enzyme were also carried out on these compounds. The antimicrobial study has shown that all the compounds are potential antibacterial agents against Gram-negative bacterial strains and better antifungal agents with respect to standard drugs used.
Effect of zinc oxide nanoparticles on anticorrosion performance has been studied in conductive polyaniline containing zinc-rich primer in 3.5wt% NaCl solution, using Electrochemical Impedance Spectroscopy (EIS) and localized electrochemical Scanning Vibrating Electrode Technique (SVET). The results showed that the addition of nano-zinc oxide particles in conductive polyaniline containing zinc-rich primer made the reaction of zinc more stable and slower, further increasing the effective cathodic protection period. EIS and SVET results confirmed that three performance evolution stages were obtained for zinc-rich primer being immersed in 3.5wt% sodium chloride solution.
Selective and sensitive detection of explosive materials through a simple approach is an attractive area of research having implications on public safety and homeland security. Considering this implication in mind, a new Ni-anthracene complex was designed and synthesized and has been demonstrated as an efficient fluorescence chemosensor for the selective and sensitive detection of 2,4,6-trinitrophenol. Firstly, a fluorescent anthracene ligand (A) was synthesized by treating anthracene-9-carboxaldehyde with 1,3-diaminopropane in presence of a weak acid. To achieve superior selectivity and great quenching efficiency for 2,4,6-trinitrophenol (TNP), a Ni complex, namely, [Ni(μ2-L)(NO3)] (B), was synthesized via the reaction of A with Ni(NO3)2·6H2O. Complex B showed strong emission peak (λmax) at 412 nm and exhibited high selectivity towards TNP among other nitroaromatics and anions. 100 equivalents of TNP made 95% fluorescence quenching of B and its detection limit for TNP was calculated as 2.8 μM.
Two-dimensional (2D) materials, such as graphene and MoS 2 , have been attracting wide interest in surface enhancement Raman spectroscopy. This perspective gives an overview of recent developments in 2D materials’ application in surface-enhanced Raman spectroscopy. This review paper focuses on the applications of using bare 2D materials and metal/2D material hybrid substrate for Raman enhancement. The Raman enhancing mechanism of 2D materials will also be discussed. The progress covered herein shows great promise for widespread adoption of 2D materials in SERS application.
Laser-induced breakdown spectroscopy (LIBS) was used for the quantitative analysis of elements present in textile dyes at ambient pressure via the fundamental mode (1064 nm) of a Nd:YAG pulsed laser. Three samples were collected for this purpose. Spectra of textile dyes were acquired using an HR spectrometer (LIBS2000+, Ocean Optics, Inc.) having an optical resolution of 0.06 nm in the spectral range of 200 to 720 nm. Toxic metals like Cr, Cu, Fe, Ni, and Zn along with other elements like Al, Mg, Ca, and Na were revealed to exist in the samples. The %-age concentrations of the detected elements were measured by means of standard calibration curve method, intensities of every emission from every species, and calibration-free (CF) LIBS approach. Only Sample 3 was found to contain heavy metals like Cr, Cu, and Ni above the prescribed limit. The results using LIBS were found to be in good agreement when compared to outcomes of inductively coupled plasma/atomic emission spectroscopy (ICP/AES).
Despite the inherent spatial confinement of multiphoton processes that arises from focusing through an objective, the maximum imaging depth in conventional multiphoton microscopy is ultimately limited by noise from out-of-focus fluorescence. This is particularly evident when imaging beyond shallow depths in highly scattering tissue as increased laser powers are necessary. The out-of-focus signal originates from multiphoton processes taking place primarily at shallow depths and deteriorates contrast and limits imaging depth. In this paper, annular laser beams are explored as a concept to reduce this background signal in multiphoton microscopy. The approach is theoretically verified by data from simulations and proof of principle is demonstrated on a custom-built experimental multiphoton microscopy platform. Annular laser beams were created by adopting wavefront control using a spatial light modulator and implemented for imaging tissue phantoms simulating turbid media and human skin ex vivo. The signal-to-background ratios were calculated and compared to images acquired with a traditional, filled-aperture Gaussian beam. Experiments in tissue phantom show an improvement in signal-to-background ratio of about 30% when using annular beam illumination in comparison to Gaussian illumination at specific depths. When laser power is not the limiting factor, this approach is expected to provide even greater benefits.
The concepts of standard analysis techniques applied in the field of Fourier spectroscopy treat fundamental aspects insufficiently. For example, the spectra to be inferred are influenced by the noise contribution to the interferometric data, by nonprobed spatial domains which are linked to Fourier coefficients above a certain order, by the spectral limits which are in general not given by the Nyquist assumptions, and by additional parameters of the problem at hand like the zero-path difference. To consider these fundamentals, a probabilistic approach based on Bayes’ theorem is introduced which exploits multivariate normal distributions. For the example application, we model the spectra by the Gaussian process of a Brownian bridge stated by a prior covariance. The spectra themselves are represented by a number of parameters which map linearly to the data domain. The posterior for these linear parameters is analytically obtained, and the marginalisation over these parameters is trivial. This allows the straightforward investigation of the posterior for the involved nonlinear parameters, like the zero-path difference location and the spectral limits, and hyperparameters, like the scaling of the Gaussian process. With respect to the linear problem, this can be interpreted as an implementation of Ockham’s razor principle.
Autofluorescence of secondary compounds contained in plant secretory cells may be applied to the analysis of medicinal plants for pharmacy. Emission and prevailing fluorescent pharmaceuticals have been estimated in several models of species such as Salvia officinalis, Berberis vulgaris, Humulus lupulus, and Matricaria chamomilla, by luminescence microscopy, microspectrofluorimetry, and confocal microscopy.
The molecular structure of the three compounds Aceclofenac (I), Salicylic Acid (II), and Piroxicam (III) has been determined using Gaussian 03W program with B3LYP method using 6-311++G (d,p) basis set calculations. The molecular structures were fully optimized with atomic numbering scheme adopted in the study. To understand the mode of binding and molecular interaction, the docking studies of compounds Aceclofenac (I), Salicylic Acid (II), and Piroxicam (III) have been carried out with prostaglandin H2 synthase-1 (1PGE) as target using induced fit docking. The molecular docking results show that the interactions and energy for Aceclofenac, Salicylic Acid, and Piroxicam show the best results when docked with prostaglandin H2 synthase-1 (1PGE). The hydrogen bonding interactions of compound I (Aceclofenac) are prominent with Arginine moiety, those of compound II (Salicylic Acid) are prominent with Tyrosine and Serine moieties, and compound III (Piroxicam) shows such interaction with Tyrosine and Arginine moieties. These interactions of prostaglandin H2 synthase-1 (1PGE) with substrates are responsible for governing COX-1 inhibitor potency which in turn is a direct measure of the potency of the drug.
Energy levels and oscillator strengths for neutral oxygen have been calculated using the Cowan (CW), SUPERSTRUCTURE (SS), and AUTOSTRUCTURE (AS) atomic structure codes. The results obtained with these atomic codes have been compared with MCHF calculations and experimental values from the National Institute of Standards and Technology (NIST) database.
This study investigates the level of technological enhancement of normally occurring radioactive materials (TENORM) in the red mud waste due to the production of alumina in Jamaica. Technological enhancements factors (TEF) were determined for the uranium, thorium, actinium series, their progenies, and the nonseries potassium-40 using gamma spectrometry. The study concluded that bauxite production technologically enhances the uranium progenies Th-234, Pb-214, Bi-214, and Pa-234 and the thorium-232 progenies Ac-228, Pb-212, and Bi-212 in red mud. The actinium series was technologically enhanced, but K-40 and the thorium daughter, Tl-208, were reduced. The spectrometric comparison of Tl-208 (at 510 keV) was unexpected since its other photopeaks at 583 keV, 934 keV, and 968 keV were markedly different. An explanation for this anomaly is discussed. An explanation regarding the process of accumulation and fractionation of organically derived phosphate deposits and potassium-feldspar is offered to explain the spectrometric differences between the alumina product and its waste material, red mud.
A series of eight water soluble anionic, cationic, and neutral zinc(II) complexes were synthesized and characterized. The interaction of these complexes with bovine serum albumin (BSA), human serum albumin (HSA), lysozyme, and free tryptophan (Trp) was investigated using steady-state fluorescence spectroscopy. Static and dynamic fluorescence quenching analysis based on Stern-Volmer kinetics was conducted, and the decrease in fluorescence intensity of the Trp residue(s) can be ascribed predominantly to static quenching that occurs when the Zn complex binds to the protein and forms a nonfluorescent complex. The role played by the nature of the ligand, the metal, and complex charge in quenching Trp fluorescence was investigated. The binding association constants (Ka) ranged from 10 4 to 10 10 M −1 and indicate that complexes with planar aromatic features have the strongest affinity for globular proteins and free Trp. Complexes with nonaromatic features failed to interact with these proteins at or in the vicinity of the Trp residues. These interactions were studied over a range of temperatures, and binding was found to weaken with the increase in temperature and was exothermic with a negative change in entropy. The thermodynamic parameters suggest that binding of Zn complexes to the proteins is a highly spontaneous and favorable process.
The thermal and chain length sensitivity of the infrared spectra of some solid state anhydrous silver(I) salts (n-octanoate ton-eicosanoate, inclusive) are discussed. At ambient temperature, the tilted alkyl chains, anchored to the metal planes via chelating bidentate coordination to the silver ions, are crystallized in the fully extendedall-transconformation. Interestingly, though all compounds are crystallized in a monoclinic crystal system, their lateral chain packing,van der Waalseffects, and hence vibrational features are chain length-dependent. This is a direct result of electrostatic effects of the COO group in addition to vibrational coupling between CH2, CH3, and COO modes, an effect which varies significantly with chain length. Variable temperature infrared measurements indicate significant irreversible changes in the metal-carboxyl coordination sphere, most likely due to bond fission. For long chain adducts (nc>12), thermally induced crystal system switching, monoclinic to triclinic, indicates greater thermal sensitivity of their alkyl chains. During heating, the regions of the hydrocarbon chains, furthest from the COO, become increasingly molten and mobile as the stepwise melt advances towards the solid COO moieties. This solid-liquid melting behaviour is responsible for mesophase formation in metal carboxylate systems.
We have critically investigated the ATR-IR spectroscopy data behavior of burned human teeth as opposed to the generally observed behavior in human bones that were subjected to heat treatment, whether deliberate or accidental. It is shown that the deterioration of the crystallinity index (CI) behavior sometimes observed in bones subjected to high temperature appears to be of higher frequency in the case of bioapatite from teeth. This occurs because the formation of theβ-tricalcium phosphate (β-TCP) phase, otherwise known aswhitlockite, clearly ascertained by the X-ray diffraction (XRD) patterns collected on the same powdered specimens investigated by ATR-IR. These results point to the need of combining more than one physicochemical technique even if apparently well suitable, in order to verify whether the assumed conditions assessed by spectroscopy are fully maintained in the specimens after temperature and/or mechanical processing.
Glucose is the universal energy source and a critical substrate for lipid synthesis in mammalian cells. Analysis of both glucose and lipid in cells is important for the understanding of the regulation of lipid synthesis in many cell types, but especially adipocytes, the major storage cell for fat in mammals. The fluorescent 7-nitrobenz-2-oxa-1,3-diazole (NBD) derivative of glucose, 2-NBDG, is used to monitor glucose uptake and the lipid-selective fluorophore Nile red is used to monitor lipid accumulation. Previous reports have used NBD-based fluorophores and Nile red simultaneously despite the possibility of spectral overlap. In this study, we determined if these fluorophores were experimentally compatible in preadipocytes and adipocytes stained with 2-NBDG and Nile red separately or costained. We found that Nile red is detectable in the wavelengths necessary to excite and detect 2-NBDG. This interference was further increased by the solvatochromic effect of lipid-localized Nile red. In addition, we found a synergistic increase in fluorescent intensity when both fluorophores were present. Unfortunately, even fine control of the excitation or emission wavelengths did not identify wavelengths suitable for selective detection when cells were costained. Therefore, 2-NBDG and Nile red cannot be used simultaneously—but can likely be used sequentially—to assess glucose uptake and lipid accumulation in lipid-laden cells.
Alcohol or ethanol is considered the most widely used recreational drug worldwide, and its production, consumption, and sale are strictly regulated by laws. Alcohol content of alcoholic beverages (wine, beers, and spirits) is about 3–50% v/v. Analytical methods to determine the alcohol content must be reliable, precise, and accurate. In this study, the amount of ethanol in several alcoholic beverages was determined using a 45 MHz low-field benchtop NMR (nuclear magnetic resonance) spectrometer. Internal standard and standard addition analytical methods were utilized to quantify ethanol. For both methods, acetic acid or acetonitrile was used as internal standard to quantify alcohol content by using the peak area corresponding to the methyl peaks of ethanol, acetic acid, or acetonitrile. Results showed that internal standard method gave values of percent alcohol that are in close agreement with the indicated label as confirmed by running the samples in a 400 MHz high-field NMR spectrometer using acetic acid as internal standard. This study demonstrates the utility of a benchtop NMR spectrometer that can provide an alternative technique to analyze percent alcohol in alcoholic products.
Electron density and ionization temperatures were measured for inductively coupled argon plasma at atmospheric pressure. Different sample introduction systems were investigated. Samples containing Sn, Hg, Mg, and Fe and acidified with hydrochloric or acetic acids were introduced into plasma in the form of aerosol, gaseous mixture produced in the reaction of these solutions with NaBH4 and the mixture of the aerosol and chemically generated gases. The electron densities measured from Hα, Hβ, Hγ, and Hδ lines on the base of Stark broadening were compared. The study of the H Balmer series line profiles showed that the ne values from Hγ and Hδ were well consistent with those obtained from Hβ which was considered as a common standard line for spectroscopic measurement of electron density. The ne values varied from 0.56·1015 to 1.32·1015 cm−3 and were the highest at loading mixture of chemically generated gases. The ionization temperatures of plasma, determined on the base of the Saha approach from ion-to-atom line intensity ratios, were lower for Sn and Hg (6500–7200 K) than those from Fe and Mg lines (7000–7800 K). The Sn II/Sn I and Hg II/Hg I, Fe II/Fe I, and Mg II/Mg I intensity ratios and the electron densities (ne) were dependent on experimental conditions of plasma generation. Experimental and theoretically calculated ionization degrees were compared.
The light induced behaviour of siloxane substituted azobenzene compounds in the presence of alkylene spacers is reported for the first time. Firstly, these photosensitive compounds were synthesized and elucidated the molecular structure by spectral analysis such as NMR, FTIR, and UV/Vis. Photoisomerization effect was evaluated in solution and also in nematic phase. The photosaturation occurred exactly at 29 seconds, whereas thermal back relaxation was observed ranging from 19.8 to 23.8 hours. Long duration of the thermal back relaxation is due to the presence of sterically hindered siloxane group substituted to the azobenzene molecules. Decrease in the duration of cis-trans isomerization was found when the number of alkylene spacers was increased. These siloxane based azobenzene derivatives are useful for the fabrication of optical storage device and molecular switches.
The possibility for double pulse LIBS in the process of a direct layer-by-layer analysis of the titanium-based PVD-coatings on polished flat blank samples of steel and silicon and also of the TiAlN/TiN-coating on a milling cutter is considered. A method is proposed to control thickness of the radiation evaporated layer by defocusing the laser beam with respect to the surface, making it possible to attain the depth resolution of 0.1 μ m. The Ti and Ti-Zr-coatings produced using the ion-assisted condensation method and subjected to streams of the nitrogen plasma in a magnetic-plasma compressor are studied.
The Tagish Lake meteorite is CI/CM2 chondrite, which fell by a fireball event in January 2000. This study emphasizes the cathodoluminescence (CL) and Raman spectroscopical properties of the Tagish Lake meteorite in order to classify the meteoritic forsterite and its relation to the crystallization processes in a parent body. The CL-zoning of Tagish Lake meteorite records the thermal history of chondrules and terrestrial weathering. Only the unweathered olivine is forsterite, which is CL-active. The variation of luminescence in chondrules of Tagish Lake meteorite implies chemical inhomogeneity due to low-grade thermal metamorphism. The blue emission center in forsterite due to crystal lattice defect is proposed as being caused by rapid cooling during the primary crystallization and relatively low-temperature thermal metamorphism on the parent body of Tagish Lake meteorite. This is in a good agreement with the micro-Raman spectroscopical data. A combination of cathodoluminescence and micro-Raman spectroscopies shows some potentials in study of the asteroidal processes of parent bodies in solar system.
