Spectroscopy Of Aqueous Solutions Research Articles

Development and validation of anin situand real-time quantification method for bicarbonate, carbonate and orthophosphate ions by ATR FT-IR spectroscopy in aqueous solutions

Bicarbonate salts are used in various industrial processes and could even serve as an alternative source of carbon in bioprocesses involving photosynthetic organisms. Industrial productions require efficient monitoring and control to ensure that their output will meet target specifications. To this end, a simple and rapid in situ quantification method was developed for bicarbonate, carbonate and phosphate ions using Attenuated Total Reflectance-Fourier Transform Infrared (ATR FT-IR) spectroscopy combined with partial least squares (PLS). The resulting multivariate approach allows the simultaneous determination of inorganic carbon and orthophosphate ions concentrations in aqueous solutions (R2 > 0.98, root-mean-square-errors of the cross validation RMSECV < 3.3%). Validation of the method was achieved through replicability and repeatability tests. Univariate calibration graphs are linear over a concentration range of 150 mM (R2 > 0.9990). Quantification limits for those ions were in the 6.9-17.2 mM range, as determined from univariate models. The multivariate model was successfully applied to a microalgal culture of Scenedesmus obliquus using bicarbonate as the carbon source and a phosphate buffer to maintain the pH. This analytical technique did not require extraction or chemical treatment and no sample preparation is needed. The results demonstrate the potential of ATR FT-IR method to study inorganic carbon and phosphate species during a bioprocess.

Unique Hydrogen Bonds in Membrane Protein Monitored by Whole Mid-IR ATR Spectroscopy in Aqueous Solution.

Protein function is coupled to its structural changes, for which stimulus-induced difference Fourier-transform infrared (FTIR) spectroscopy is a powerful method. By optimizing the attenuated total reflection (ATR)-FTIR analysis on sodium-pumping rhodopsin KR2 in aqueous solution, we first measured the accurate difference spectra upon sodium binding in the whole IR region (4000-1000 cm-1). The new spectral window allows the analysis of not only the fingerprint region (1800-1000 cm-1) but also the hydrogen-bonding donor region (4000-1800 cm-1), revealing an unusually strong hydrogen bond of Tyr located in the sodium binding site of KR2. Progress in ATR-FTIR difference spectroscopy provides an approach to investigating stimulus-induced structural changes of membrane proteins under physiological aqueous conditions.

Reactivity of prehydrated electrons toward nucleobases and nucleotides in aqueous solution.

DNA damage induced via dissociative attachment by low-energy electrons (0 to 20 eV) is well studied in both gas and condensed phases. However, the reactivity of ultrashort-lived prehydrated electrons ([Formula: see text]) with DNA components in a biologically relevant environment has not been fully explored to date. The electron transfer processes of [Formula: see text] to the DNA nucleobases G, A, C, and T and to nucleosides/nucleotides were investigated by using 7-ps electron pulse radiolysis coupled with pump-probe transient absorption spectroscopy in aqueous solutions. In contrast to previous results, obtained by using femtosecond laser pump-probe spectroscopy, we show that G and A cannot scavenge [Formula: see text] at concentrations of ≤50 mM. Observation of a substantial decrease of the initial yield of hydrated electrons ([Formula: see text]) and formation of nucleobase/nucleotide anion radicals at increasing nucleobase/nucleotide concentrations present direct evidence for the earliest step in reductive DNA damage by ionizing radiation. Our results show that [Formula: see text] is more reactive with pyrimidine than purine nucleobases/nucleotides with a reactivity order of T > C > A > G. In addition, analyses of transient signals show that the signal due to formation of the resulting anion radical directly correlates with the loss of the initial [Formula: see text] signal. Therefore, our results do not agree with the previously proposed dissociation of transient negative ions in nucleobase/nucleotide solutions within the timescale of these experiments. Moreover, in a molecularly crowded medium (for example, in the presence of 6 M phosphate), the scavenging efficiency of [Formula: see text] by G is significantly enhanced. This finding implies that reductive DNA damage by ionizing radiation depends on the microenvironment around [Formula: see text].

Ultrafast kinetics of linkage isomerism in Na2[Fe(CN)5NO] aqueous solution revealed by time-resolved photoelectron spectroscopy.

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of time-resolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation.

English

The optical transition probabilities and hetero-association of caffeine with norfloxacin were obtained using UV-Vis spectroscopy in aqueous solution at room temperature (295K). The heter-association constant of norfloxacin-caffeine complexes (6.67×103 M-1) was obtained using Benesi-Hildebrand approach by linear curve fitting to the experimental data. In order to characterize the binding system of the compounds, the thermodynamic parameters were investigated using Vant’s Hoff equation at the temperature ranges (295 to 304K) with a change in enthalpy value (-1.277±0.103 kJ.mol-1.K-1). The values of change in the thermodynamic parameters indicated that the electrostatic forces play the major role in the binding reaction between the molecules of norfloxacin-caffeine complexes. In addition, the optical transition probabilities of norfloxacin were also calculated in the wavenumber regions from (20000 to 40000 cm-1) by using integrated absorption coefficient techniques. This study is very important for understanding the binding reaction in biological system, nature and strength of the transition, absorption spectral interpretation, and in providing stringent test of atomic and molecular structure calculations for theoretical work of the compounds. Key words: Norfloxacin, caffeine, hetero-association, optical transition, thermodynamics, UV-Vis spectroscopy.

Quantum Dynamics and Spectroscopy of Ab Initio Liquid Water: TheInterplay of Nuclear and Electronic Quantum Effects.

Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable challenges of treating the quantum nature of both the electrons and nuclei. Exploiting our recently developed methods that provide acceleration by up to 2 orders of magnitude, we combine path integral simulations with on-the-fly evaluation of the electronic structure at the hybrid density functional theory level to capture the interplay between nuclear quantum effects and the electronic surface. Here we show that this combination provides accurate structure and dynamics, including the full infrared and Raman spectra of liquid water. This allows us to demonstrate and explain the failings of lower-level density functionals for dynamics and vibrational spectroscopy when the nuclei are treated quantum mechanically. These insights thus provide a foundation for the reliable investigation of spectroscopy and reactivity in aqueous environments.

Complex formation of mercury(II) chloride with dipeptides

Mixed-ligand complex formation in the HgCl–L systems (L= GlyGly, AlaAla) has been studied by pH potentiometry, calorimetry, and 1Н and 13С NMR spectroscopy in aqueous solutions at 298.15 K and ionic strengths I of 0.5 (KNO3). The thermodynamic parameters of formation of Hg n Cl p L q H–r (n = 1; p = 0, 1, 2; q = 1, 2; r = 0, 1, 2) complexes have been determined. The most probable coordination modes of the dipeptide molecules in the mixed-ligand complexes were discussed.

English

The self-association, optical transition probabilities, and hetero-association with chlorogenic acid of nicotinamide were obtained from UV-Vis spectroscopy in aqueous solution at room temperature (293K). The dimerization constant of nicotinamide ( ) was obtained using dimer model by nonlinear curve fitting technique. The hetero-association constant in the system of molecules of nicotinamide with chlorogenic acid were obtained in aqueous solution using a Benesi-Hildebrand equation. In order to characterize the binding system of the dimerization reactions for the self and hetero-association of the compound, the thermodynamic parameters were investigated using Vant’s Hoff equation at the temperature range (293 to 299K). As a result, the change of enthalpy obtained for the self and hetero-association is and respectively. The values of change in the thermodynamic parameters indicated that the hydrophobic interaction and electrostatic forces subsequently plays the major role in the binding reaction between the molecules of nicotinamide and its complexes with chlorogenic acid, respectively. In addition, the optical transition probabilities of nicotinamide were also calculated in the wavenumber regions by using integrated absorption coefficient techniques. Finally, the results of this study are very important for understanding the binding reaction in biological system, nature and strength of the transition in molecular interaction, absorption spectral interpretation, and in providing stringent test of atomic and molecular structure calculations in theoretical work of the compounds. Key words: Nicotinamide, chlorogenic acid, self-association, hetero-association, optical transition probabilities, thermodynamic properties, UV-Vis spectroscopy.

Encapsulation of 2,2′-(decane-1,10-diyl)-diisoquinoline into cucurbit[6]uril and α,α′,δ,δ′-tetramethyl-cucurbit[6]uril: formation of pseudorotaxanes and polypseudorotaxanes†

Host–guest complexation of cucurbit[6]uril and α,α′,δ,δ′-tetramethyl-cucurbit[6]uril with 2,2′-(decane-1,10-diyl)-diisoquinolinium has been investigated by 1H NMR, UV and fluorescence spectroscopy in aqueous solution and by X-ray crystallography in solid state. Experimental data suggest that in the aqueous solution, both host molecules form [2]pseudorotaxanes with the host located over the decyl chain of the guest. In the solid state, neighbouring [2]pseudorotaxanes are linked by π⋯π and C–H⋯π interactions, eventually generating polypseudorotaxanes.

Simultaneous Determination of Monoatomic Ions via Infrared Attenuated Total Reflection Spectroscopy in Aqueous Solution at Different Temperatures.

In this study, monoatomic and thus IR-inactive ions were determined via infrared attenuated total reflection (IR-ATR) spectroscopy including Cl(-), Na(+), Mg(2+), Ca(2+), K(+) and Br(-), next to the IR-active ion [Formula: see text] The determination of IR-inactive ions is enabled, as each ion influences the infrared spectrum of bulk water by organizing the water molecules within the solvation shell around the ionic species in a unique way. Furthermore, the influence of temperature was taken into account for the potential application of this analytical technique in real-world scenarios. Using chemometric data analysis, seven ions could be discriminated at temperatures ranging between 3 ℃ and 45 ℃. Finally, within a sample of seawater, Cl(-), Na(+), Mg(2+) and [Formula: see text] could be simultaneously quantified, while the concentrations of Ca(2+), K(+) and Br(-) remained below the achievable limits of detection.

Toward a new paradigm for sonochemistry: Short review on nonequilibrium plasma observations by means of MBSL spectroscopy in aqueous solutions

This review summarizes recent studies of multibubble sonoluminescence (MBSL) in aqueous media in order to highlight new insights into the origin of the sonochemical activity. The observation of OH(C2Σ+–A2Σ+) emission band and a spectroscopic analysis of OH(A2Σ+–X2Πi) emission band in MBSL of water pre-equilibrated with noble gases revealed the formation of a nonequilibrium plasma inside the collapsing bubble (Te>Tv>Tr, where Te is an electron temperature, Tv is a vibrational temperature and Tr is a rotational (gas) temperature). The Te and Tv estimated using OH(A2Σ+–X2Πi) emission band increase with ultrasonic frequency. In Xe the Tv of OH(A2Σ+) state is much higher than in Ar most probably due to the lower ionization potential of Xe. The MBSL of C2∗ Swan band (d3Πg–a3Πu) measured in aqueous tert-butanol (t-BuOH) solutions correlates with the data obtained for OH(A2Σ+–X2Πi) emission band. Analysis of the gaseous products of t-BuOH sonolysis revealed a significant sonochemical activity even at high t-BuOH concentration when MBSL is totally quenched, indicating that drastic intrabubble conditions (plasma) are not necessarily accompanied by sonoluminescence. The nonequilibrium plasma model of cavitation allows to explain the reverse carbon isotope effect observed during the sonolysis of water in the presence of Ar/CO gas mixture.

Electrochemical Oxidation of Alizarin Red-S on Glassy Carbon Electrode: Mechanistic Study, Surface Adsorption and Preferential Surface Orientation

The electrochemical oxidation of alizarin red-S has been studied using cyclic and differential pulse voltammetry, double step chronocoulometry and impedance spectroscopy in aqueous solution on glassy carbon electrode. The results revealed that alizarin red-S shows one oxidation peak and two reduction peaks. Electrochemical adsorption of alizarin red S was also studied in more details on glassy carbon surface. Double layer charge was calculated by chronocoulometric measurement in two ways, by using organic solvent for diminishing surface adsorption and by using a blank solution without alizarin red S. Obtained results showed that alizarin red-S adsorbed on glassy carbon in multi-layer arrays. Computational calculations were done by Chem Bio 3D software and Gaussian software on B3LYP/6-311++ (d, p) level of theory.

ω-Tbo-IT1-New Inhibitor of Insect Calcium Channels Isolated from Spider Venom.

Novel disulfide-containing polypeptide toxin was discovered in the venom of the Tibellus oblongus spider. We report on isolation, spatial structure determination and electrophysiological characterization of this 41-residue toxin, called ω-Tbo-IT1. It has an insect-toxic effect with LD50 19 μg/g in experiments on house fly Musca domestica larvae and with LD50 20 μg/g on juvenile Gromphadorhina portentosa cockroaches. Electrophysiological experiments revealed a reversible inhibition of evoked excitatory postsynaptic currents in blow fly Calliphora vicina neuromuscular junctions, while parameters of spontaneous ones were not affected. The inhibition was concentration dependent, with IC50 value 40 ± 10 nM and Hill coefficient 3.4 ± 0.3. The toxin did not affect frog neuromuscular junctions or glutamatergic and GABAergic transmission in rat brains. Ca2+ currents in Calliphora vicina muscle were not inhibited, whereas in Periplaneta americana cockroach neurons at least one type of voltage gated Ca2+ current was inhibited by ω-Tbo-IT1. Thus, the toxin apparently acts as an inhibitor of presynaptic insect Ca2+ channels. Spatial structure analysis of the recombinant ω-Tbo-IT1 by NMR spectroscopy in aqueous solution revealed that the toxin comprises the conventional ICK fold containing an extended β-hairpin loop and short β-hairpin loop which are capable of making “scissors-like mutual motions”.

(2) H and (139) La NMR Spectroscopy in Aqueous Solutions at Geochemical Pressures.

Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust.

A liquid flatjet system for solution phase soft-x-ray spectroscopy.

We present a liquid flatjet system for solution phase soft-x-ray spectroscopy. The flatjet set-up utilises the phenomenon of formation of stable liquid sheets upon collision of two identical laminar jets. Colliding the two single water jets, coming out of the nozzles with 50 μm orifices, under an impact angle of 48° leads to double sheet formation, of which the first sheet is 4.6 mm long and 1.0 mm wide. The liquid flatjet operates fully functional under vacuum conditions (<10−3 mbar), allowing soft-x-ray spectroscopy of aqueous solutions in transmission mode. We analyse the liquid water flatjet thickness under atmospheric pressure using interferomeric or mid-infrared transmission measurements and under vacuum conditions by measuring the absorbance of the O K-edge of water in transmission, and comparing our results with previously published data obtained with standing cells with Si3N4 membrane windows. The thickness of the first liquid sheet is found to vary between 1.4–3 μm, depending on the transverse and longitudinal position in the liquid sheet. We observe that the derived thickness is of similar magnitude under 1 bar and under vacuum conditions. A catcher unit facilitates the recycling of the solutions, allowing measurements on small sample volumes (∼10 ml). We demonstrate the applicability of this approach by presenting measurements on the N K-edge of aqueous NH4+. Our results suggest the high potential of using liquid flatjets in steady-state and time-resolved studies in the soft-x-ray regime.

Synthesis and characterization of benzimidazolium-functionalized polysulfones as anion-exchange membranes

Anion-exchange membranes containing pendant benzimidazolium groups were synthesized from polysulfone by chrolomethylation followed by nucleophilic substitution reaction with 1-methylbenzimidazole. The structures of the polymers were characterized by 1H-NMR and FTIR analysis. The resulting membranes showed high thermal stability below 200 °C. The values of water uptake and swelling degree increased with the ion-exchange capacity of the polymeric membrane. The ionic conductivity was measured by means of impedance spectroscopy in aqueous solution of potassium hydroxide (10−4−10−1 M). The results show not only a clear correlation between the membrane's electrochemical behavior with the electrolyte solution embedded in the membrane, but also with the degree of the polysulfone's chloromethylation.Thus, the ionic conductivity increased more than two orders of magnitude when the degree of chloromethylation increased from 40 to 140%. Benzimidazolium-functionalized polysulfones exhibited better thermal, mechanical, and electrochemical properties than the widely used polymeric membranes containing quaternary ammonium groups. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2363–2373

Effect of host–guest complex formation on the fluorescence of 6-methoxy-1-methyl-quinolinium cation with 4-sulfonatocalix[4]arene: utilization as a fluorescent probe for the study of difenzoquat binding

The complexation of the highly fluorescent 6-methoxy-1-methyl-quinolinium (C1MQ) and the widely used herbicide, difenzoquat (DFQ), with 4-sulfonatocalix[4]arene (SCX4) macrocycle was studied by isothermal titration calorimetry, fluorescence and NMR spectroscopy in aqueous solutions at 298 K. Both guests produced 1:1 complexes with SCX4, but the binding affinity of C1MQ was more than one order of magnitude larger than that of DFQ in neutral medium. The higher stability of C1MQ-SCX4 complex originated from the significant enthalpy gain upon its formation. The encapsulation of C1MQ in SCX4 in the ground state resulted in an efficient fluorescence quenching due to electron transfer from the host to the excited guest. The marked difference in the fluorescence quantum yields for free and bound C1MQ was used to detect the competitive complexation of DFQ in SCX4.

Amphiphilic acrylamide-based copolymer with porphyrin pendants for the highly selective detection of Hg2+ in aqueous solutions

A novel amphiphilic acrylamide-based polymer with porphyrin pendants that was prepared from radical copolymerization of 5-(p-acryloyloxyphenyl)-10,15,20-triphenylporphyrin (AOTPP) and N,N-dimethylacrylamide (DMAM) has been first reported as a highly selective and sensitive optochemical sensor for Hg2+. The responsive optical properties of the polymer were investigated by UV–vis absorption spectroscopy in aqueous solutions. Upon adding Hg2+, a new peak at 456 nm in the Soret band of porphyrin molecule was induced and gave rise to a visible color change from brown–red to green, which was attributed to the formation of unique aggregates intrigued by the coordinative interaction between Hg2+ and porphyrin groups. Moreover, there is nearly no interference observed from other metal ions (Na+, Mg2+, K+, Zn2+, Ca2+, Cr3+, Co2+, Ni2+, Pb2+, Cu2+, Al3+ and Fe3+), thus indicating the excellent sensing selectivity towards Hg2+ by the sensor. On the basis of the relationship of absorbance changes and Hg2+ concentrations, the polymeric sensor is allowed for quantitative analysis of Hg2+ ion with a low detection limit of 50 nM.

Synthesis and spectrophotometric studies of water-soluble amino[bis(ethanesulfonate)] azobenzene pH indicators

Three azobenzene pH indicators with amino[bis(ethanesulfonate)] substituents were synthesized and studied by UV–visible absorption spectroscopy in aqueous solution. The indicators exhibit brilliant and distinct colour changes with transitions between pH 1 and 4. Significant changes were observed in the UV–visible spectra on titration with acid with pKa values ranging from 2.2 to 2.8. The indicators demonstrate individual changes in colour as a function of pH. These novel pH indicators complement the existing library of azobenzene indicator dyes and may be useful for environmental situations with high proton concentrations.

Deswelling and Electrolyte Dissipation in Free Diffusion of Charged PAMAM Dendrimers.

The diffusion coefficient of charged PAMAM dendrimers was measured by fluorescence correlation spectroscopy in aqueous solution at submicromolar concentrations. The solution pH was varied for conditions ranging from a fully charged to neutral charge dendrimer to infer about electrostatic swelling in the dilute regime. The diffusion coefficient of generation G4 increases by as much as 20% between high and low charge conditions due to the combined effects of polyelectrolyte deswelling and loss of electrolyte dissipation. By taking into account the electrolyte dissipation in the friction factor, we have found that the observed deswelling corresponds to a change of hydrodynamic radius between 7-13% for generation G4 and about 12% for generation G7. Simulations of molecular dynamics of dendrimer G4 show that counterion uptake by the dendrimer structure upon full protonation induces a 16% increase of its radius of gyration. The change in dendrimer size is slightly larger than that previously reported from neutron scattering techniques, thereby suggesting that electrostatic swelling is more pronounced at dilute dendrimer concentration and low ionic strength. It is confirmed that even higher generations, which have more congested molecular structures, can experience some degree of conformational change in response to a change of the dendrimer charge density.