The 1H and 13C NMR chemical shifts of Strychnos alkaloids revisited at the DFT level

The density functional theory calculation of ¹H and ¹³C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated ¹H and ¹³C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

Development and validation of a reversed‐phase HPLC method for CYP1A2 phenotyping by use of a caffeine metabolite ratio in saliva

CYP1A2 is important for metabolizing various clinically used drugs. Phenotyping of CYP1A2 may prove helpful for drug individualization therapy. Several HPLC methods have been developed for quantification of caffeine metabolites in plasma and urine. Aim of the present study was to develop a valid and simple HPLC method for evaluating CYP1A2 activity during exposure in xenobiotics by the use of human saliva. Caffeine and paraxanthine were isolated from saliva by liquid‐liquid extraction (chlorophorm/isopropanol 85/15v/v). Extracts were analyzed by reversed‐phase HPLC on a C₁₈ column with mobile phase 0.1% acetic acid/methanol/acetonitrile (80/20/2 v/v) and detected at 273nm. Caffeine and paraxanthine elution times were <13min with no interferences from impurities or caffeine metabolites. Detector response was linear (0.10–8.00µg/ml, R²>0.99), recovery was >93% and bias <4.47%. Intra‐ and inter‐day precision was <5.14% (n=6). The limit of quantitation was 0.10µg/ml and the limit of detection was 0.018±0.002µg/mL for paraxanthine and 0.032±0.002µg/ml for caffeine. Paraxanthine/caffeine ratio of 34 healthy volunteers was significantly higher in smokers (p<0.001). Saliva paraxanthine/caffeine ratios and urine metabolite ratios were highly correlated (r=0.85, p<0.001). The method can be used for the monitoring of CYP1A2 activity in clinical practice and in studies relevant to exposure to environmental and pharmacological xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd.     

Microstructural stability and age-hardening behavior of Re-added dual two-phase Ni3Al and Ni3V intermetallic alloys

The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni₃Al (L1₂) and Ni₃V (D0₂₂) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures.     

Highly Luminescent Red Phosphorescent OLED with Interfacial Layers for Hole Transport and Electron Injection

Four kinds of red phosphorescent organic light-emitting devices were fabricated and compared to investigate the effect of interfacial layers for hole transport and electron injection. 1 nm-thick LiF in the device A and C and 1 nm-thick Cs₂CO₃ in the device B and D were deposited as an electron injection layer between the anode and the electron transport layer, and 5 nm-thick layer of dipyrazion[2,3-f:2′,2′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile[HATCN] was inserted as a hole transport interfacial layer between the hole injection layer and the hole transport layer only in the device C and D. Under a luminance of 1000 cd/m², the power efficiencies were 7.6 lm/W and 8.5 lm/W in the device A and B, and 8.6 lm/W and 13.4 lm/W in the device C and D. The quantum efficiency of the device D was 15.8% under 1000 cd/m² which was somewhat lower than those of the device A and C, but a little higher than that of the device B. The luminance of the device D was much higher than those of the other devices at a given votage. The luminance of the device D at 7 V was 23,710 cd/m², which was 13.0, 3.4, and 4.0 times higher than those of the device A, B, and C at the same voltage, respectively.     

Gas-phase 21Ne NMR studies and the nuclear magnetic dipole moment of neon-21

Gas-phase ²¹Ne nuclear magnetic resonance spectra were measured at the natural abundance of ²¹Ne isotope for samples consisting of pressurized neon up to 60 bar at room temperature and applying the magnetic field of the strength B₀ = 11.7574 T. It showed that the nuclear magnetic resonance frequency is linearly dependent on the density of gaseous neon. The resonance frequency was extrapolated to the zero-density point, and it permitted the determination of the ²¹Ne nuclear magnetic moment, μ(²¹Ne) = 0.6617774(10) μ_N. The present value of μ(²¹Ne) is not influenced by the bulk magnetic susceptibility of neon and interactions between neon atoms; therefore, it is more precise and reliable than the previous result obtained for μ(²¹Ne).     

Surface passivation in n-type silicon and its application in silicon drift detector

Based on the surface passivation of n-type silicon in a silicon drift detector(SDD), we propose a new passivation structure of SiO2/Al2O3/SiO2 passivation stacks. Since the SiO2 formed by the nitric-acid-oxidation-of-silicon(NAOS)method has good compactness and simple process, the first layer film is formed by the NAOS method. The Al2O3 film is also introduced into the passivation stacks owing to exceptional advantages such as good interface characteristic and simple process. In addition, for requirements of thickness and deposition temperature, the third layer of the SiO2 film is deposited by plasma enhanced chemical vapor deposition(PECVD). The deposition of the SiO2 film by PECVD is a low-temperature process and has a high deposition rate, which causes little damage to the device and makes the SiO2 film very suitable for serving as the third passivation layer. The passivation approach of stacks can saturate dangling bonds at the interface between stacks and the silicon substrate, and provide positive charge to optimize the field passivation of the n-type substrate.The passivation method ultimately achieves a good combination of chemical and field passivations. Experimental results show that with the passivation structure of SiO2/Al2O3/SiO2, the final minority carrier lifetime reaches 5223 μs at injection of 5×10¹⁵ cm^-3. When it is applied to the passivation of SDD, the leakage current is reduced to the order of nA.