Spectroscopic and structural characterization of Na2[(VO)2(ttha)]·8H2O (ttha = triethylenetetraamine-N,N,N′,N″,N′″,N′″-hexaacetate): Interpreting the results with density functional theory

Na₂[(V^IVO)₂(ttha)]·8 H₂O (ttha = triethylenetetraamine–N,N,N′,N″,N′″,N′″–hexaacetate ion), prepared by treating [VO(H₂O)₅][(VO)₂(ttha)]·4 H₂O with Na₆(ttha), has been characterized by single crystal X-ray diffraction, infrared spectroscopy, UV–Vis absorption spectroscopy, electron spin resonance spectroscopy, and modeled by density functional theory (DFT). The X-ray structure revealed a distorted octahedral geometry around each vanadium center. The electronic absorption spectrum of [(VO)₂(ttha)]²⁻ (aq) features absorptions at ca. 200 nm (ε > 13900 L mol⁻¹ cm⁻¹), 255 nm (ε = 3480 L mol⁻¹ cm⁻¹), 586 nm (ε = 33 L mol⁻¹ cm⁻¹), and 770 nm (ε = 38 L mol⁻¹ cm⁻¹). The time-dependent density functional theory (TDDFT) calculated electronic absorption spectrum was remarkably similar to the actual spectrum, and TDDFT predicts absorption peaks at 297, 330, 458, 656, and 798 nm. TDDFT assigned the peak at 798 nm to be the α spin HOMO → LUMO transition. Hence, the peak at 770 nm in the actual spectrum is most likely the α spin HOMO → LUMO transition. Moreover, the TDDFT calculations revealed that the α spin HOMO and LUMO are partly comprised of d orbitals on both vanadium centers, and the first derivative electron spin resonance spectrum also suggests that the two unpaired electrons in [(VO)₂(ttha)]²⁻ are localized near the vanadium centers.     

Electrogenerated chemiluminescence from thiol-capped CdTe quantum dots and its sensing application in aqueous solution

In this paper, the electrogenerated chemiluminescence (ECL) from thiol-capped CdTe quantum dots (QDs) was reported. The ECL emission was occurred at −1.1 V and reached a maximum value at −2.4 V when the potential was cycled between 0.0 and −2.5 V. The reduced species of CdTe QDs could react with the coreactants to produce the ECL emission. The CdTe QD concentration (6.64 × 10⁻⁷ mol L⁻¹) of ECL is lower than that (1.0 × 10⁻³ mol L⁻¹) of chemiluminescence (CL). Based on the enhancement of light emission from thiol-capped CdTe QDs by H₂O₂ in the negative electrode potential, a novel method for the determination of H₂O₂ was developed. The light intensity was linearly proportional to the concentration of H₂O₂ between 2.0 × 10⁻⁷ and 1.0 × 10⁻⁵ mol L⁻¹ with a detection limit of 6.0 × 10⁻⁸ mol L⁻¹. Compared with most of previous reports, the proposed method has higher sensitivity for the determination of H₂O₂. In addition, the ECL spectrum of thiol-capped CdTe QDs exhibited a peak at around 620 nm, which was substantially red shifted from the photoluminescence (PL) spectrum, suggesting the surface states play an important role in this ECL process.     

Ultrasound assisted ambient temperature synthesis of ternary oxide AgMO2 (M=Fe, Ga)

The application of ultrasound for the synthesis of ternary oxide AgMO₂ (M=Fe, Ga) was investigated. Crystalline α-AgFeO₂ was obtained from the alkaline solutions of silver and iron hydroxides by sonication for 40 minutes. α-AgFeO₂ was found to absorb optical radiation in the 300-600 nm range as shown by diffuse reflectance spectroscopy. The Raman spectrum of α-AgFeO₂ exhibited two bands at 345 and 638 cm⁻¹. When β-NaFeO₂ was sonicated with aqueous silver nitrate solution for 60 minutes, β-AgFeO₂ possessing orthorhombic structure was obtained as the ion-exchanged product. The Raman spectrum of β-AgFeO₂ showed four strong bands at 295, 432, 630 and 690 cm⁻¹. Sonication of β-NaGaO₂ with aqueous silver nitrate solution for 60 minutes resulted in olive green colored, α-AgGaO₂. The diffuse reflectance spectrum and the EDX analysis confirmed that the ion-exchange through sonication was complete. The Raman spectrum of α-AgGaO₂ had weak bands at 471 and 650 cm⁻¹.     

Detection of P. aeruginosa using nano-structured electrode-separated piezoelectric DNA biosensor

A DNA biosensor for detection of Pseudomonas aeruginosa was set up based on the modification of two membranes (nano-TiO₂ and nano-TiO₂-polyethylene glycol hybrid membrane) to the ESPS surface. These two membrane materials were synthesized by sol-gel method. The detection was accomplished by modifying ss-DNA on the sensitive membrane and then hybridizing with their complementary strands from the P. aeruginosa in liquid phase. UV spectrum was used to identify the purity and concentration of extracted DNA; IR spectrum and SEM were used to characterize the properties of the membrane. The detection was highly improved by adoption of nanotechnology and hybrid membrane. Less than 3 h was sufficient. The detection linear range was from 10⁻¹ to 10⁻³ g l⁻¹ and the limit of detection was 10⁻⁴ g l⁻¹.     

Urea and thiourea based efficient colorimetric sensors for oxyanions

Urea and thiourea based receptors 1 and 2 bind H₂PO₄⁻, OH⁻, CH₃CO₂⁻, and PhCO₂⁻ ions in an acetonitrile/DMSO (9:1, v/v) medium. Binding of these anions causes an appreciable change in the visible region of the spectrum, which can be detected by the naked eye. The affinity constant for H₂PO₄⁻ is higher by about an order of magnitude as compared to the other oxyanions mentioned above. Ab initio calculations predicted tweezer-like binding modes for receptors 1 and 2 with these anions and a higher affinity toward H₂PO₄⁻ was predicted in acetonitrile.     

Spectroscopic, thermal, magnetic and structural characterization of K3VF6 prepared at room temperature

A straight forward room-temperature synthesis of V(III) containing complex fluoride K₃VF₆, using KF and vanadium(III) acetylacetonate is reported. The pale green colored powder was characterized by chemical analysis, powder X-ray diffraction; diffuse reflectance spectroscopy, infrared spectroscopy, Raman spectroscopy, differential scanning calorimetry, scanning electron microscopy, photoluminescence spectroscopy, magnetic susceptibility measurements and photoluminescence spectroscopy. The powder X-ray diffraction pattern was fitted in P2₁/n space group (monoclinic) with a = 12.106 (1) Å, b = 17.685 (0) Å, c = 11.802 (0) Å, β = 92.23° (1). Differential scanning calorimetry showed phase transitions, occurring at 158 °C and 190 °C. In the FT-IR spectrum, characteristic band for the VF₆³⁻ group was observed at 508 cm⁻¹. The bands observed in the 335-361 cm⁻¹ region and at 504 cm⁻¹ in the room temperature Raman spectrum of K₃VF₆ corresponded to the F_2g and A_1g modes, respectively. The ratio of the frequencies (F_2g/A_1g) observed in the diffuse reflectance spectrum was fitted on the Tanabe-Sugano diagram to determine the Racah parameter B value of 712 cm⁻¹. Magnetic ordering was not observed down to the lowest measured temperature of 5 K.     

Gamma radiation induced synthesis of gold nanoparticles in aqueous polyvinyl pyrrolidone solution and its application for hydrogen peroxide estimation

Gold nanoparticles (Au nps) have been synthesized in aqueous solution of polyvinyl pyrrolidone (PVP) by gamma radiolysis from HAuCl₄·3H₂O precursor and in presence of small concentrations of Ag⁺, 2-propanol and acetone. The effect of different experimental parameters, such as concentration of reactant, molecular weight of PVP on nanoparticle formation was studied. TEM image confirmed that spherical Au nps were formed when PVP of molecular weight 360,000 Da was used as capping agent. H₂O₂ is a reactant in the enzyme catalyzed reaction of o-phenylene diamine (o-PDA). The reaction product has a weak absorption in the yellow region of the spectrum. When this product interacts with Au nps, it leads to enhancement of the absorption peak. The nanoparticles synthesized by radiation method were used for estimation of H₂O₂. The absorbance value of this peak at λ_max was observed to change with H₂O₂ concentration, which was monitored for estimation of H₂O₂. The response is linear in the range of 2.5×10⁻⁶ mol dm⁻³ to 2×10⁻⁴ mol dm⁻³ and 1×10⁻⁷ mol dm⁻³ to 3×10⁻⁶ mol dm⁻³ H₂O₂ in two separate sets of experimental parameters with detection limit 1×10⁻⁷ mol dm⁻³.     

The EPR spectrum of O on magnesium oxide

The EPR spectrum of O⁻ on MgO has been observed following the reaction of N₂O with electrons trapped at the surface. The spectrum of the ion in axial symmetry is characterized by g_⊥ = 2.041 and g_∥ = 2.0016. Upon exposure to H₂, CO, CO₂ or additional N₂O the spectrum is replaced by another having g₁ = 2.0172, g₂ = 2.0100 and g₃ = 2.0014. This spectrum is tentatively assigned to the O₃⁻ ion.     

Vibrational spectroscopy of the sorosilicate mineral hemimorphite Zn4(OH)2Si2O7 · H2O

Raman spectroscopy complimented by infrared spectroscopy has been used to study the mineral hemimorphite from different origins. The Raman spectra show consistently similar spectra with only one sample showing additional bands due to the presence of smithsonite. Raman bands observed at 3510–3565 and 3436–3455 cm⁻¹ are assigned to OH stretching vibrations. Using a Libowitzky type formula, these OH bands provide hydrogen bond distances of 0.2910, 0.2825, 0.2762 and 0.2716 pm. Water bending modes are observed in the Raman spectrum at 1633 cm⁻¹. An intense Raman band at 930 cm⁻¹ is attributed to SiO symmetric stretching vibration of the Si₂O₇ units. Raman bands observed at 451 and 400 cm⁻¹are attributed to out-of-plane bending vibrations of the Si₂O₇ units. Raman bands at 330, 280, 168 and 132 cm⁻¹ are assigned to ZnO and OZnO vibrations.     

Energy exchange processes in a low temperature N2CO transfer laser

A liquid-nitrogen-cooled, active-N₂-pumped CO laser has produced cw oscillation from ν = 2 → ν = 1 (4.8 μm) to ν = 35 → ν = 34 (8.0 μm). An analysis of the output spectrum gives the VT relaxation rate of CO (ν ≈30) by He at 150°K as 2 × 10³ sec⁻¹ torr⁻¹.     

A novel nonenzymatic sensor based on LaNi0.6Co0.4O3 modified electrode for hydrogen peroxide and glucose

In this paper, LaNi_0.6Co_0.4O₃ (LNC) nanoparticles were synthesized by the sol–gel method, and the structure and morphology of LNC nanoparticles were characterized by X-ray diffraction spectrum, scanning electron microscopy and transmitting electron microscopy. And then, LNC was used to modify carbon paste electrode (CPE) without any adhesive to fabricate hydrogen peroxide and glucose sensor, and the results demonstrated that LNC exhibited strong electrocatalytical activity by cyclic voltammetry and amperometry. In H₂O₂ determination, linear response was obtained in the concentration range of 10 nM–100 μM with a detection limit of 1.0 nM. In glucose determination, there was the linear region of 0.05–200 μM with a detection limit of 8.0 nM. Compared with other reports, the proposed sensor also displayed high sensitivity toward H₂O₂ (1812.84 μA mM⁻¹ cm⁻²) and glucose (643.0 μA mM⁻¹ cm⁻²). Moreover, this prepared sensor was applied to detect glucose in blood serum and hydrogen peroxide in toothpaste samples with satisfied results, indicating its possibility in practical application.     

A Raman spectroscopic study of the phosphate mineral pyromorphite Pb5(PO4)3Cl

A series of selected pyromorphite minerals Pb₅(PO₄)₃Cl from different Australian localities has been studied by Raman spectroscopy complemented with selected infrared spectroscopy. The Raman spectrum of unsubstituted pyromorphite shows a single band at around 920 cm⁻¹ but for the natural minerals two bands at 919 and ∼932 cm⁻¹ attributed to the ν₁ (PO₄)³⁻ stretching vibration. The observation of multiple bands is attributed to the non-equivalence of phosphate units in the pyromorphite structure and the reduction in symmetry of the (PO₄)³⁻ units. This symmetry reduction is confirmed by the observation of multiple bands in both the ν₄ bending region (500–595 cm⁻¹) and the ν₂ bending region (350–500 cm⁻¹). The presence of isomorphic substitution of (PO₄)³⁻ by (AsO₄)³⁻ units is identified by the ν₁ symmetric stretching bands at around 824 and 851 cm⁻¹ and the ν₂ bending region around 331 and 354 cm⁻¹. Contrary to expectation Raman bands in the 3320–3700 cm⁻¹ region are observed and assigned to OH stretching bands of OH units resulting from the substitution of chloride anions in the pyromorphite structure. This study brings in to question the actual formula of natural pyromorphite as it is better represented as Pb₅(PO₄,AsO₄)₃(Cl,OH) · xH₂O.     

Quenching of the OH and nitrogen molecular emission by methane addition in an Ar capacitively coupled plasma to remove spectral interference in lead determination by atomic fluorescence spectrometry

A new method is proposed to remove the spectral interference on elements in atomic fluorescence spectrometry by quenching of the molecular emission of the OH radical (A²Σ⁺ → X²Π) and N₂ second positive system (C³Π_u → B³Σ_g) in the background spectrum of medium power Ar plasmas. The experiments were carried out in a radiofrequency capacitively coupled plasma (275 W, 27.12 MHz) by CH₄ addition. The quenching is the result of the high affinity of OH radical for a hydrogen atom from the CH₄ molecule and the collisions of the second kind between nitrogen excited molecules and CH₄, respectively. The decrease of the emission of N₂ second positive system in the presence of CH₄ is also the result of the deactivation of the metastable argon atoms that could excite the nitrogen molecules. For flow rates of 0.7 l min^− 1 Ar with addition of 7.5 ml min^− 1 CH₄, the molecular emission of OH and N₂ was completely removed from the plasma jet spectrum at viewing heights above 60 mm. The molecular emission associated to CH and CH₂ species was not observed in the emission spectrum of Ar/CH₄ plasma in the ultraviolet range. The method was experimented for the determination of Pb at 283.31 nm by atomic fluorescence spectrometry with electrodeless discharge lamp and a multichannel microspectrometer. The detection limit was 35 ng ml^− 1, 2–3 times better than in atomic emission spectrometry using the same plasma source, and similar to that in hollow cathode lamp microwave plasma torch atomic fluorescence spectrometry.     

High-pressure Raman spectra of l-histidine hydrochloride monohydrate crystal

Single-crystals of l-histidine hydrochloride monohydrate, C₆H₉N₃O₂·HCl·H₂O, were studied by Raman spectroscopy as a function of pressure in a diamond anvil cell up to 7.5 GPa at room temperature over the spectral range 3450-30 cm⁻¹. The effect of changing pressure on the vibrational spectrum is discussed. From the analysis of results we inferred that the crystal undergoes a reversible structural phase transition between 2.7 and 3.1 GPa. This transition is characterized by the splitting of a band related to torsion of CO₂⁻, the disappearance and appearance of modes related with stretching of OH⁻ and deformation of CO₂⁻, as well as with bands of low wavenumber which are assigned as lattice modes, and by the discontinuities of the curves of wavenumber versus pressure. Pressure coefficients for all modes observed in this work are also given.     

Raman spectroscopy of arsenolite: crystalline cubic As4O6

The complete Raman spectrum of arsenolite, cubic crystalline As₄O₆, is reported for the first time. The previously unseen E_g mode has been found at 443 cm⁻¹. Further, there is additional support for the assignment of the 415 cm⁻¹ mode as T_2g.     

Complexes of Al(III) with d-gluconic acid

The complexation of Al(III) with d-gluconic acid was studied in solution by means of pH-potentiometry, ESI mass spectrometry and one- and two-dimensional NMR spectroscopy. Six complexes were found to form in solution from pH 2 to 10: [AlL]²⁺, [AlLH₋₁]⁺, [AlLH₋₂], [AlLH₋₃]⁻, [AlL₂H₋₁] and [AlL₂H₋₂]⁻. NMR spectroscopy indicated very complicated chemical exchange processes between the free ligand and gluconic acid molecules bound in the metal complexes, with different coordination modes resulting in changes both of the chemical shift and of the line shape of the signals. A solid complex [AlL₂H₋₁] · 2H₂O was isolated as a microcrystalline powder and characterized. The structures of the complexes are discussed on the basis of the spectroscopic results and MM force field calculations.     

Studies on lithium acetate doped chitosan conducting polymer system

The structure of chitosan contains the amine group that can act as electron donors. Complexation between chitosan and the salt can be proven by infrared and X-ray photoelectron spectroscopy methods. The NH₂, NH₃⁺ and OC-NHR vibrations which can be observed at 1590, 1560 and 1650 cm⁻¹ shift to lower wave numbers when the complexes are formed. The after deconvolution Li 1s core level spectrum of the chitosan-salt complexes can contain several gaussian components one of which has a binding energy peak at 55.2 eV which signifies Li-N interaction. The component that peaks at ∼403 eV in the N 1s core level spectrum complements the proof of N-Li interaction. The highest conductivity achieved for a plasticized chitosan-salt complex is of the order 10⁻⁶ S/cm using lithium acetate as the doping salt. Transference number studies prove that this material is ionic conductor and from transient ionic current studies that mobility of the ions is of the order of 10⁻⁴ cm²/V s.     

Flow injection chemiluminescence determination of isoniazid using luminol and silver nanoparticles

The effect of silver colloidal nanoparticles (AgNPs) on the luminol–isoniazid system was investigated. It was found that AgNPs could act as a nanocatalyst on the luminol–isoniazid system to generate chemiluminescence (CL). The CL emission spectrum of the luminol–isoniazid–AgNPs system showed a peak with a maximum at 425 nm. It was suggested that the luminophor species was the excited state 3-aminophthalate. The reduction of dissolved O₂ to H₂O₂ by isoniazid and decomposition of H₂O₂ to the oxygen-related radicals were attributed to the catalytic effect of AgNPs. Under optimized conditions, the CL signal intensity was linear with the isoniazid concentration in the range of 10–1000 ng mL^{− 1}, with the correlation coefficient of 0.9996. The limit of detection was 2.7 ng mL^{− 1} isoniazid. The relative standard deviations for seven repeated measurements of 60 and 200 ng mL^{− 1} isoniazid were 1.4 and 2.4%, respectively. The effect of potent interfering compounds on the CL signal intensity of the proposed luminol–isoniazid–AgNPs system was investigated. The proposed method was successfully applied to the determination of isoniazid in a pharmaceutical sample.     

Single-run ion chromatographic separation of inorganic and low-molecular-mass organic anions under isocratic elution: Application to environmental samples

For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 μm particle size), Allsep A-2 (7 μm particle size), and IC SI-50 4E (5 μm particle size). A complete baseline separation for all analyzed anions (i.e., F⁻, acetate, formate, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na₂CO₃ and 1.0 mM NaHCO₃ with a flow rate of 1.0 mL min⁻¹. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na₂CO₃ plus 1.0 mM NaHCO₃ with a flow rate of 1.2 mL min⁻¹. Therefore, it was necessary to adapt a second run with a 2.0 mM Na₂B₄O₇ solution as an eluent under a flow rate of 0.8 mL min⁻¹ for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na₂CO₃ plus 1.5 mM NaHCO₃ with a flow rate of 1.6 mL min⁻¹, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L⁻¹ for F⁻, Ac⁻, For⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.     

Aurichalcite – An SEM and Raman spectroscopic study

Raman spectroscopy complimented with supplementary infrared spectroscopy has been used to characterise the vibrational spectrum of aurichalcite a zinc/copper hydroxy carbonate (Zn,Cu²⁺)₅(CO₃)₂(OH)₆. XRD patterns of all specimens show high orientation and indicate the presence of some impurities such as rosasite and hydrozincite. However, the diffraction patterns for all samples are well correlated to the standard reference patterns. SEM images show highly crystalline and ordered structures in the form of micron long fibres and plates. EDAX analyses indicate variations in chemical composition of Cu/Zn ratios ranging from 1/1.06 to 1/2.87. The symmetry of the carbonate anion in aurichalcite is C_s and is composition dependent. This symmetry reduction results in multiple bands in both the symmetric stretching and bending regions. The intense band at 1072 cm⁻¹ is assigned to the ν₁(CO₃)²⁻ symmetric stretching mode. Three Raman bands assigned to the ν₃(CO₃)²⁻ antisymmetric stretching modes are observed for aurichalcite at 1506, 1485 and 1337 cm⁻¹. Multiple Raman bands are observed in 800–850 cm⁻¹ and 720–750 cm⁻¹ regions and are attributed to ν₂ and ν₄ bending modes confirming the reduction of the carbonate anion symmetry in the aurichalcite structure. An intense Raman band at 1060 cm⁻¹ is attributed to the δ OH deformation mode.