Novel experimental design paradigm for development of eco-friendly gradient chromatographic method for simultaneous determination of metronidazole and spiramycin

This work describes the innovative experimental design-assisted development of a green gradient chromatographic method for concomitant analysis of metronidazole (MTR) and spiramycin (SPR). Two different designs including fractional factorial and Box-Behnken designs were implemented for screening and optimization steps, respectively. The optimum chromatographic conditions involved a mobile phase consisting of ethanol and 20 mM sodium dihydrogen phosphate solution (pH adjusted to 2.5) in the ratio 2:98 (v/v) for 2 min then the ratio changed to 30:70 (v/v). The flow rate was 1.3 mL/minute. Separation and analysis were performed on X-bridge C18 (150 mm × 4.6 mm × 3.5 μm) column with diode array detector set at 230 nm. Column oven temperature was 40°C. A linear response was acquired over the range of 5–125 μg/mL for both drugs. Detection and quantitation limits were 0.86 and 2.62 μg/mL for MTR and 0.92 and 2.83 μg/mL for SPR, respectively. The method was implemented for determination of both drugs in three tablet formulations. The method was proved to be green as evaluated by three assessment tools. The application of experimental designs assists in development of a robust green chromatographic method in gradient elution mode for determination of both drugs within reasonable time.     

Simultaneous quantitative determination of insulin aspart and insulin degludec in human plasma using simple shoot LC method

Combining short-acting and long-acting insulin analogs was a real challenge that was overcome by NovoNordisk through the co-formulation of insulin aspart and insulin degludec in single-dosage form. The proposed study provides a simple, short, and reliable HPLC method with diode array detection that is developed and validated for the simultaneous determination of insulin aspart and insulin degludec in human plasma. The proposed method achieved good separation between the two analytes utilizing a C8 column at 35°C in a very short run time (6 min), with a simple, low-cost, and reliable extraction method through precipitation of plasma protein. Gradient elution was applied using a mobile phase consisting of 0.1 M sodium sulfate (pH 3.4) and acetonitrile. The method was validated according to EMA Guideline on Bioanalytical Validation. The proposed method had a linear range from 3.0 to 300 μg/mL for insulin aspart and from 3.5 to 300 μg/mL for insulin degludec. The intra- and inter-day precision of insulin aspart were 0.36–3.33% and 1.59–8.84%, respectively, and accuracy was between 10.06 and 3.09% The intra- and inter-day precision of insulin degludec were 0.29–1.93% and 0.89–5.14%, respectively, and accuracy was between −5.29 and 3.91%.     

Covalent and ionic Cu(II) complexes with cyclam and substituted benzoato ligands: structural,thermal, redox and mesomorphic properties

A covalent mononuclear complex, [Cu(p–HOC₆H₄COO)₂(cyclam)] (1), and two ionic mononuclear complexes, [Cu(cyclam)(H₂O)₂](p–CH₃OC₆H₄COO)₂ (2) and [Cu(cyclam)(H₂O)₂](p–CH₃(CH₂)₁₅OC₆H₄COO)₂·H₂O (3), were formed from reaction of cyclam with [Cu₂(p–HOC₆H₄COO)₄(H₂O)₂], [Cu₂(p–CH₃OC₆H₄COO)₄(H₂O)₂] and [Cu₂(p-CH₃(CH₂)₁₅OC₆H₄COO)₄(H₂O)₂], respectively. These complexes were isolated as purple crystals with molecular structures showing distorted octahedral N₄O₂ geometry. Complexes 1 and 2 were irreversibly reduced to Cu(I) and oxidized to Cu(III), while 3 was redox inactive. Complex 2 reacted with N-(hexadecyl)isonicotinamide (L) to form [Cu(cyclam)(L)₂](p–CH₃OC₆H₄COO)₂ (4). These complexes were thermally stable (T_dec > 200 °C for 1–3 and 174 °C for 4). Complexes 3 and 4 behaved as ionic liquids (melting temperatures lower than 100 °C) and exhibited mesomorphism.     

Using Bezier curves for the calculation of retention indices of polycyclic aromatic hydrocarbons in the so-called Lee's scale in temperature-programmed gas chromatography with mass spectrometry detection

The retention indices of some polycyclic aromatic hydrocarbons (PAHs) separated by temperature-programmed gas chromatography are computed by smoothing reference data with Bezier curves of orders 6 are more consistent with the scheme of this retention parameter, and they present standard deviations systematically smaller than those associated with classical retention indices. The Bezier curve possesses the property of local control, (i.e., their graphs are modified only in the neighbourhood of the displaced point). The values thus obtained were compared with the corresponding ones calculated in a classical way. Detailed statistical analysis is presented to describe the retention indices of PAHs expressed in the so-called Lee's scale as a function of retention temperatures (in degrees C). As a training set, experimental retention data of PAHs obtained on a PE-5 phase is used for correlation. As prediction sets, literature experimental retention indices expressed in the so-called Lee's scale obtained on a DB-5 slightly polar stationary phase are applied for comparison. The method developed is successfully used for estimating and predicting the capillary gas chromatography retention index of PAHs.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

1.315μm附近CO2的高分辨率吸收光谱

 利用可调谐激光长程吸收光谱测量系统，记录到1.315μm附近高气压（80kPa和40kPa）CO₂的高分辨率吸收光谱，拟合分析获得谱线参数，结果与HITRAN 2k的数据基本一致。用程差法测量了绝对吸收，氧碘激光频率(7 603.138 5cm^-1)的总吸收截面为(0.23~0.29)×^-24cm²。仅计算谱线吸收的吸收截面为0.18×10^-24cm²。在1.315μm波段COCO₂存在连续吸收，吸收截面为(0.05~0.11)×10^-24cm²。还讨论了测量误差问题。     

μ-Synchrotron radiation excited X-ray fluorescence microprobe trace element studies on spherules of the Cretaceous/Tertiary boundary transitions of NE-Mexico and Haiti samples

Synchrotron radiation, collimated to a μm scale was used for the determination of trace elements in micro-tektites and spherule material for the first time. The experimental set-up of the SXRF microprobe at beamline L at HASYLAB at DESY offers a suitable method for performing non-destructive in situ multi-element analysis focusing on spatial trace element distributions and mineral phases of the melted ejecta material from the Cretaceous/Tertiary boundary. The spatial distribution of trace elements was determined in melt inclusions as well as in phase transitions in selected parts of chlorite–smectite spherules and tektite glass material by using a beam with a diameter of 15 μm collimated with a glass capillary for line- and area scans as well as for single point measurements for elements with Z between 19 and 92. The analyzed spherules show alteration features but also zonation and carbonate inclusions, originating from the Chicxulub impact event. These initial results demonstrate the potential of μ-SXRF analysis for the discrimination of alteration and primary signals of the spherules and re-construction of their genetic evolution. It could be shown that the spherules represent a complex mixture of different materials from the subsurface at the Chicxulub impact site.     

Aquation kinetics of chloropentamminecobalt (III) perchlorate in dicarboxylate media containing 10% (v/v) acetone

The aquation kinetics of [Co(NH₃)₅Cl]²⁺ in dicarboxylate media containing 10% (v/v) acetone is measured in the temperature range of 35–60°C. A new empirical correlation between the rate coefficient, k_obs, and the stoichiometric concentration of the dicarboxylate ligand (C_L) has been established and a reaction mechanism is proposed. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 311–316, 1997.