Characterization of warfarin unusual peak profiles on oligoproline chiral high performance liquid chromatography columns

Unusual peak profiles of warfarin were characterized on two oligoproline chiral stationary phases (CSPs). The pattern of 1st peak (S(−)) broadening and the 2nd peak (R(+)) compression was observed under mobile phase of hexane (0.1% TFA)/2-propanol (IPA) on a triproline CSP 1, and with other alcohol modifier such as ethanol, 1-propanol, 1-butanol, 2-butanol, and tert-butanol as well. Through analyzing system peak of additives, the unusual peak profile was interpreted by perturbation of TFA additive system peak. The unusual peak profile was also found in enantioseparation of coumachlor and on a covalently bonded doubly tethered diproline CSP 2. The pattern of 1st peak (S(−)) broadening and the 2nd peak (R(+)) compression can change to pattern of 1st peak compression and the 2nd peak broadening from 15 to 50 °C. Chiral separation of warfarin created nonlinear van’t Hoff plots on CSP. No peak broadening/compression were observed with methyl tertiary butyl ether or ethyl acetate as the modifier. The peak shapes of the two warfarin enantiomers can thus be tuned by varying alcohol concentration and column temperature. High separation factor and resolution may be carried out to tune the peak profiles into Langmuir/anti-Langmuir band-shape composition. Using none hydrogen donor modifier may avoid interference of the TFA system peak.     

Electrochemical oxidation of 9-methylxanthine

The electrochemical oxidation of 9-methylxanthine proceeds via four voltammetric oxidation peaks at the pyrolytic graphite electrode. The first voltammetric oxidation peak (peak I_a) is a 1e reaction giving a radical which dimerizes to 8,8′-bi-9-methyl-9H-purine-2,6-(1H, 3H)-dione. Peak II_a is a further 2e electrooxidation of the peak I_a dimer to another yellow dimer 8,8′-bi-9-methyl-9H-purine-2,6-(1H)-dione-3,5-(3H)-diiminylidene. This dimer is not very stable and it hydrolyzes to 1-methyl allantoin. Peak III_a is an adsorption pre-peak to peak IV_a which corresponds, overall, to a direct 4e?4H⁺ electrooxidation of 9-methylxanthine to an unstable diimine of 9-methyluric acid. Hydrolysis of this diimine leads to a variety of ultimate products.     

First-principles relativistic calculation for 4f-5d transition energy of Ce in various fluoride hosts

In this paper, we investigated the 4f-5d transition energy of Ce³⁺ in various fluoride hosts based on the first-principles discrete-variational Dirac-Slater (DV-DS) calculations using Slater's transition-state theory. Especially, we focused on the lowest energy peak (1st peak) of 4f-5d transition for Ce³⁺ impurities. As the host crystals, we adopted the 15 fluorides, for which the experimental data of the lowest energy peak (1st peak) in 4f-5d transitions were available from literature except for NaMgF₃ and BaMgF₄. A high correlation between the experimental 1st peak energies and the theoretical ones was obtained which suggests a possibility to predict the 4f-5d transition energy of Ce³⁺ in various fluoride hosts using the first-principles calculation.     

Quantitation of ion abundances in fourier transform ion cyclotron resonance mass spectrometry

To improve the analytical usefulness of Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), an extensive survey of various methods for quantitation of peak magnitudes has been undertaken using a series of simulated transient response signals with varying signal-to-noise ratio. Both peak height (five methods) and peak area (four methods) were explored for a range of conditions to determine the optimum methodology for quantitation. Variables included dataset size, apodization function, damping constant, and zero filling. Based on the results obtained, recommended procedures for optimal quantitation include: apodization using a function appropriate for the peak height ratios observed in the spectrum (i.e., Hanning for ratios of about 1:10, three-term Blackman-Harris for ratios of ～1:100, or Kaiser-Bessel for ratios of ～1:1000); zero filling until the peaks of interest are represented by 10–15 points (generally obtained with one order of zero filling); and use of the polynomial y=(ax ²+bx+c) ⁿ and the three data points of highest intensity of the peak to locate the peak maximum, Y _max=(?b ²/4a+c) ⁿ . In this peak fitting procedure, which we have termed the “Comisarow method,” n is 5.5, 9.5, and 12.5 for the Hanning, three-term Blackman-Harris, and Kaiser-Bessel apodization functions, respectively. Accuracy of quantitation using an optimal peak height determination is about equal to that for peak area measurements. These recommendations were found to be valid when tested with real FTICR-MS spectra of xenon isotopes.     

Extension of the two-dimensional mass channel cluster plot method to fast separations utilizing low thermal mass gas chromatography with time-of-flight mass spectrometry

Implementation of a data reduction and visualization method for use with high-speed gas chromatography and time-of-flight mass spectrometry (GC-TOFMS) is reported. The method, called the “2D m/z cluster method” facilitates analyte detection, deconvolution, and identification, by accurately measuring peak widths and retention times using a fast TOFMS sampling frequency (500 Hz). Characteristics and requirements for high speed GC are taken into consideration: fast separations with narrow peak widths and high peak capacity, rapid data collection rate, and effective peak deconvolution. Transitioning from standard GC (10–60+ minute separations) to fast GC (1–10 min separations) required consideration of how to properly analyze the data. This report validates use of the 2D m/z cluster method with newly developed GC technology that produces ultra-fast separations (∼1 min) with narrow analyte peak widths. Low thermal mass gas chromatography (LTM-GC) operated at a heating rate of 250 °C/min coupled to a LECO Pegasus III TOFMS analyzed a 115 component test mixture in 120 s with peak widths-at-base, w_b (4σ), of 350 ms (average) to produce a separation with a high peak capacity, n_c ∼ 340 (at unit resolution R_s = 1). The 2D m/z cluster method is shown to separate overlapped analytes to a limiting R_s ∼ 0.03, so the effective peak capacity was increased nearly 30-fold to n_c ∼10,000 in the 120 s separation. The method, when coupled with LTM-GC-TOFMS, is demonstrated to provide unambiguous peak rank (i.e. the number of analytes per overlapped peak in the total ion current (TIC)), by visualizing locations of pure and chromatographically overlapped m/z. Hence, peak deconvolution and identification using MCR-ALS (multivariate curve resolution – alternating least squares) is demonstrated.     

Recognizing chromatographic peaks with pattern recognition methods : Part 1. Development of a k-nearest-neighbour technique

Problems in automated peak recognition in chromatography are discussed. An algorithm based on the k-nearest neighbour technique is proposed. Recognition of a peak is done by comparing it with a predefined profile function (normally a Gaussian peak profile). The profile and a part of the chromatogram are both interpreted as points in a multi-dimensional pattern space. The distance between the two points gives the value of the peak recognition function. The effects of different properties of chromatographic peaks (i.e., peak width, peak height and noise) and of the profile parameter (i.e., dimension of the pattern space, shape and width of the function, and characteristics of the distance measure) are evaluated. The method has excellent properties for recognizing peaks with low signal/noise (S/N) ratios; an example with S/N = 1 is shown. Changing peak widths and drifting baselines have little effect on the recognition ability. Difficulties with changing peak heights can be compensated by range scaling. Problems occur when two peaks are not sufficiently separated.     

Small-angle maxima and cation-cation distances. Differences between iron nitrate and perchlorate solutions

X-ray diffraction data of aqueous solutions of iron(III) nitrate show a small-angle peak at an s value of about 0.5–0.9 A^?1. A constant relationship between peak position and concentration leads to reject the hypothesis of a quasi-lattice structure for the solutions investigated. On the contrary, no peak is present in the same s range of diffraction data of iron (III) perchlorate solutions.     

A highly selective ratiometric fluorescent chemosensor for Zn2+ ion based on a polyimine macrocycle

A new ratiometric fluorescent chemosensor based on a polyimine macrocycle ligand 1 has been synthesized. The chemosensor can exhibit a pronounced fluorescence response and high selectivity to Zn²⁺ ion over other 15 metal ions, including Cd²⁺. Sensor 1 appears an emission peak at 370 nm. Upon the addition of Zn²⁺ ion, the typical emission peak for 1 at 370 nm is obviously quenched, but a new emission peak at around 470 nm appears and shows a large enhancement due to the formation of a 1:1 Zn²⁺-1 complex. In addition, there is a good linear relationship between the fluorescence ratio I_470nm/I_370nm and the concentration of Zn²⁺, which makes a ratiometric assay of Zn²⁺ ion possible.     

Raman studies of pressure tuning of the fermi resonance in solid CO2

Raman studies on the v₁, 2v₂ Fermi doublet in solid CO₂ up to 100 kbar at ambient temperature show the upper peak to increase and the lower peak to decrease both in intensity and frequency. It is concluded that the bare v₁ is above the bare 2v₂ at all pressures in solid CO₂.     

Electrochemically inactive organic substance influence on peak height in anodic stripping voltammetry

A simplified method was proposed for calculation of changes of peak height (i) vs. deposition time (t_e) in the presence of a surfactant acting only at the deposition stage. The simplification was based on the assumption that the deposition current has a constant value until time t₁ when it decreases abruptly to a lower level. Hence the dependency of the peak height on the deposition time can be written:i=β₀t₁+β₁(t_e?t₁) Limiting cases were discussed: t₁→0 and β₁→1 leading to three types of i vs. t_e relation. The experimental evaluation was carried out for Pb(II), Cu(II) and Cd(II) in the presence of various polyethyleneglycols. All three types of curves were obtained in the experiments, as well as some which did not fit the simplified theory.     

Anodic overoxidation of poly-p-phenylene in aqueous electrolytes

Poly-p-phenylene (PPP), synthesized chemically by the Kovacič method, was mixed with 7.5% carbon black and used as a pressed thin-layer electrode (100 μm) on Pt mesh. Its overoxidation as an anode in aqueous acid electrolytes (8–18 M H₂SO₄, 8–11.3 M HClO₄, 8 M HBF₄) was investigated systematically.Slow cyclic voltammetry reveals that the reversible redox peak 1, leading to an insertion compound up to 1 F per mole (C₆H₄)₆, is following by a large second peak 2 at more positive potentials, corresponding to about 15 F with respect to the unit mentioned above. Peak separation increases with increasing acid concentration due to a negative shift of the insertion potential (peak 1) by 60 mV mol⁻¹ dm³, but normal Nernst behaviour is observed in the case of peak 2. The strong decay of the current efficiency for reversible cycling of PPP at concentrations below 10 M can be understood readily from these findings. The overoxidation starts with the formation of the polymer radical cation, which is oxidized further to the quinone, then to the product of ring opening and finally to the product of cleavage of the polymer chain. The final product seems to be a derivative of maleic acid. The p-quinone path is preferred over the o-quinone path, quite contrary to the case with graphite. The practical consequences with respect to battery application are discussed in detail.     

Voltammetric study on interaction of cysteine with type I-collagen in the aqueous medium

Interaction of cysteine with type I-collagen from bovine achilles tendon in the aqueous solutions has been examined using square wave voltammetry (SWV) and cyclic voltammetry (CV) techniques. In the absence of cysteine, type I-collagen gives a reversible peak at ?0.114 V in Britton-Robinson (B-R) buffer (pH 4.0). The electrochemical parameters (I _p/f, E _p/f, E _p/pH, I _p/pH, I _p/v, I _p/v^1/2) of type I-collagen have been also studied. In addition, it has been determined that there is a linear relationship between current and concentration of type I-collagen. On the other hand, cysteine exhibits a reversible peak at ?0.383 V due to the reduction of mercurous cysteine thiolate. By using a hanging mercury drop electrode in aqueous solutions, SWV and CV voltammograms obtained for type I-collagen in the presence of cysteine indicate that there is an interaction between type I-collagen and cysteine. In the presence of cysteine, peak current of type I-collagen decreases and a new peak is observed at ?0.121 V for cysteine which is bonded to type I-collagen.     

S K and P K absorption spectra and electronic structures of layered thiophosphates MPS3

The S K and P K absorption spectra of layered thiophosphates MPS₃ (M = Mg, Mn, Fe, Ni, Zn, Cd, Sn) were measured. The general features of the S K absorption spectra resemble one another, but the intensity ratio of the first peak to a higher energy structure and the energy position of a shoulder vary, depending on the metal species. All the P K absorption spectra exhibit a prominent peak in the neighborhood of the threshold. It is found that (1) the spectra mainly reveal the p-like partial density of states of the unoccupied energy levels of a [P₂S₆]^4- cluster and (2) the first peak arises predominantly from the electronic transitions to the antibonding levels of the PS bonds. The electronic structures and the optical spectra are discussed.     

Determination of pK a of N-alkyl-N,N-dimethylamine-N-oxides using 1H NMR and 13C NMR spectroscopy

The pK _a values of N-alkyl-N,N-dimethylamine-N-oxides were determined from the pH dependences of chemical shifts in ¹H NMR and ¹³C NMR spectra. The dependences were measured at concentrations below and above the critical micelle concentration of the amine oxides. Above the critical micelle concentration, the plots of the peak positions vs. pH were either sigmoid (the groups close to the nitrogen) or “peak type” (farther groups). The sigmoidal behaviour was a direct result of the acid-base reaction; on the other hand, the “peak type” behaviour was probably an indirect consequence of the pH variation, mediated with the change in micelle size.     

Evaluation of a Vancomycin-Based LC Column in Enantiomeric Separation of Atenolol: Method Development, Repeatability Study and Enantiomeric Impurity Determination

An LC method was developed and validated for the enantioselective separation and enantiomeric impurity quantitation of atenolol. Separation of the atenolol enantiomers on the Chirobiotic V2 (150 mm × 4.6 mm, 5 μm) column was best achieved using a ternary mobile phase of methanol–acetonitrile-triethylamine acetate 0.5% (w/v), pH 4.5 in a ratio of (45:50:5; v/v/v). Good resolution value of R _s  = 3 was obtained at a flow rate of 1 mL min^?1 within a total run time of less than 40 min. Peak identification was achieved using the standard reference of individual enantiomers. The peak of the impurity was eluted in front of the peak of the main enantiomer. Detection was performed by UV at 226 nm. Within and between day’s repeatabilities for both retention time and peak area were investigated at three concentration levels and found to be low. The method was also found to be efficient for the determination of atenolol enantiomeric impurity. An impurity quantitation level of (R)-atenolol down to 0.08% relative to the main enantiomer (S)-atenolol was found possible.     

Infrared spectra of carbon monoxide adsorbed on a smooth gold electrode Part I. EMIRS spectra in acid and alkaline solutions

Electrochemically modulated infrared spectroscopy (EMIRS) was applied to the study of adsorption of CO on gold in 0.5 M sulfuric acid and 1 M sodium hydroxide solutions. A CO stretch band was observed with a peak intensity of ca. 0.2 % between 1850 and 2000 cm⁻¹ in 1 M NaOH, while a very weak band was detected between 1950 and 2050 cm⁻¹ in 0.5 M H₂SO₄. The bands were assigned to linear CO species adsorbed on the gold surface. In 1 M NaOH, electrooxidation of the strongly adsorbed CO species, which was detected by EMIRS, starts from ca. 0.5 V (RHE) with a sharp voltammetric current peak at 1.0 V at 50 mV/s, while electrooxidation of the bulk CO starts from ca. 0 V in the absence of the strongly adsorbed CO species on Au. The strongly adsorbed CO species acts as a poison for the electrooxidation of CO in the lower potential region.     

Ab initio configuration interaction calculations of the NIs (NO2) core-hole states of p-nitroaniline

The NIs (NO₂) core-hole states of p-nitroaniline are calculated by a Cl procedure that takes account of both orbital relaxation and correlation effects. A satellite peak arising from the excitation 4b₁(Π) → 5b₁(Π) is calculated to occur 26 eV from the main ionization peak, with a relative intensity of 66%. These results are compared with gas-phase photoelectron spectra.     

Investigation of anharmonicity in rotational phonon mode for BaWO4 crystal

Spontaneous Raman spectra in the BaWO₄ were measured in the temperature range from 4 K to 280 K, and the temperature dependence of the linewidth of the A_g (191 cm⁻¹) Raman mode was analyzed using the lattice dynamical perturbative approach and one-phonon density of states (PDOS). The linewidth slope for the 191 cm⁻¹ peak for an external mode is 7.2 times larger than that for the 926 cm⁻¹ peak for a breathing mode. The different behaviors of these two modes in the case of temperature broadening could be attributed to the large energy band gap in the one-phonon density of states (PDOS) resulting in different anharmonic interactions. The origin may be that the ratio of up-conversion TDOS to down-conversion TDOS for Eg mode (191 cm⁻¹) is more than that for A_g (926 cm⁻¹). The peak of the Eg mode (191 cm⁻¹) is attributed to the coupling mode both a rotation of the Barium and an out-of-phase rotation of the oxygen in x–y plane as a librational mode.     

Numerical simulation of voltammetry focusing on the effect of initial concentration of products in reversible systems with complex stoichiometry

The effect of initial concentration of products in a general reaction of reversible process with complex stoichiometry expressed as mO + ne^? ai qR was evaluated using numerical simulations with various complex stoichiometric coefficients m and q of oxidized (O) and reduced (R) species, respectively, and with various initial concentrations. In the simulations, the transform of voltammograms according to changes in the initial concentrations were characterized by the parameter ??? (= c ₀*(D _O)^1/2/c _R* (D _R)^1/2) for any stoichiometric system. Based on the simulation results, empirical relations were obtained for (1) peak potential involving parameters for stoichiometry (m and q) and for the initial conditions (???), and (2) peak current.     

The structure and ordering of ε-MnO2

The presence of ε-MnO₂ as a major component of electrolytic manganese dioxide (EMD) has been demonstrated by a combined X-ray diffraction/transmission electron microscopy (TEM) study. ε-MnO₂ usually has a partially ordered defect NiAs structure containing 50% cation vacancies; these vacancies can be fully ordered by a low temperature (200 °C) heat treatment to form a pseudohexagonal but monoclinic superlattice.Numerous fine-scale anti-phase domain boundaries are present in ordered ε-MnO₂ and cause extensive peak broadening and a massive shift of a very intense, 0.37 nm superlattice peak. This suggests a radically different explanation of the ubiquitous, very broad ∼0.42 nm peak (∼21-22° 2θ, CuKα radiation) in EMDs, which heretofore has been attributed to Ramsdellite containing numerous planar defects. This work confirms the multi-phase model of equiaxed EMDs proposed by Heuer et al. [ITE Lett. 1(6) (2000) B50; Proc. Seventh Int. Symp. Adv. Phys. Fields 92 (2001)], rather than the defective single-phase model of Chabre and Pannetier [Prog. Solid State Chem. 23 (1995) 1] and Bowden et al. [ITE Lett. 4(1) (2003) B1].