A Comparative Study of the Semiconductor Behavior of Organic Thin Films: TCNQ-Doped Cobalt Phthalocyanine and Cobalt Octaethylporphyrin

The structure formed by cobalt phthalocyanine (CoPc) and cobalt octaethylporphyrin (CoOEP) with electron-acceptor tetracyano-π-quinodimethane (TCNQ), was studied by Density Functional Theory (DFT) methods. According to theoretical calculations, both cobalt systems can establish dispersion forces related to TCNQ and also in both cases the link between them is built by means of hydrogen bonds. Based on the results of these DFT calculations, we developed experimental work: the organic semiconductors were doped, and the thermal evaporation technique was used to prepare semiconductor thin films of such compounds. The structure of the films was studied by FTIR and Raman spectroscopy. The optical properties of the CoPc-TCNQ and CoOEP-TCNQ films were investigated by means of UV-Vis measurements. The results obtained were used to estimate the type of transitions and the optical bandgap. The results were compared to the previously calculated theoretical bandgap. The CoOEP-TCNQ film presented the smallest theoretical and experimental bandgap. Finally, the electrical properties of the organic semiconductors were evaluated from a PET (polyethylene terephthalate)/indium tin oxide (ITO)/cobalt macrocycle-TCNQ/silver (Ag) device we prepared. The CoOEP-TCNQ-based device showed an ohmic behavior. The device manufactured from CoPc-TCNQ also showed an ohmic behavior at low voltages, but significantly changed to SCLC (space-charge limited conductivity) at high voltage values.     

Monte Carlo simulations of magnetic particle suspensions with a simple assessment method for the particle overlap between magnetic spheroids

We have developed a simple assessment method for the overlap between spheroidal particles, which neither requires the complex manipulation of vectors and matrices that is indispensable in the ordinary methods, nor is based on a model potential. Moreover, we have developed an evaluation method for the interaction energy arising from the overlap of the steric layer coating spheroidal particles. This is based on a sphere-connected particle model, but some modifications are introduced in order to express an appropriate repulsive interaction energy at the deepest overlapping position. We have investigated the phase change in a magnetic spheroidal particle suspension for a two-dimensional system by means of Monte Carlo simulations. In the case of no external magnetic field, if the magnetic particle-particle interaction is sufficiently strong to favour cluster formation, long raft-like clusters tend to be formed in a dilute situation. With decreasing values of area fraction, a chain-like structure in a dense situation transforms into a raft-like structure within a narrow range of the particle area fraction. Similarly, the raft-like clusters are preferred in a weak applied magnetic field, but an increase in the field strength induces a phase change from a raft-like into a chain-like structure.

Highlights of the present paper:

1. A simple assessment method has been proposed for the overlap between two spheroidal particles.

2. The particle overlap assessment is free from a complex mathematical manipulation regarding vectors and matrices.

3. A modified sphere-connected model has been proposed in order to more accurately evaluate a repulsive interaction due to the overlap of the steric layers coating spheroidal particles.

4. 2D Monte Carlo simulations have been performed to elucidate the phenomenon of a phase change by magnetic spheroidal particles on a material plane surface.

5. A phase change between a raft-like and a chain-like aggregate structure is able to be controlled by the area fraction of particles and an external magnetic field.

     

Certain fractional calculus and integral transform results of incomplete ℵ-functions with applications

In this paper, we study certain interesting and useful properties of incomplete $\aleph$-functions. The incomplete $\aleph$-function is an extension of the $\aleph$-function. We find several useful classical integral transforms of these functions. Further, we examine the fractional calculus with the incomplete $\aleph$-functions and point out several special cases. Finally, we give the applications of incomplete $\aleph$-functions in detecting glucose supply in human blood.     

Multifunctional Sulfur-Hyperdoped Silicon Nanoparticles with Engineered Mid-Infrared Sulfur-Impurity and Free-Carrier Absorption

Si nanoparticles (NPs), which are innovative promising light-harvesting components of thin-film solar cells and key-enabling biocompatible theranostic elements of infrared-laser and radiofrequency hyperthermia-based therapies of cancer cells in tumors and metastases, are significantly advanced in their near/mid-infrared band-to-band and free-carrier absorption via donor sulfur-hyperdoping during high-throughput facile femtosecond-laser ablative production in liquid carbon disulfide. High-resolution transmission electron microscopy and Raman microscopy reveal their mixed nanocrystalline/amorphous structure, enabling the extraordinary sulfur content of a few atomic percents and very minor surface oxidation/carbonization characterized by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. A 200-nm thick layer of the nanoparticles exhibits near−mid-infrared absorbance, comparable to that of the initial 380-micron thick n-doped Si wafer (phosphor-dopant concentration ≈10¹⁵ cm⁻³), with the corresponding extinction coefficient for the hyperdoped NPs being 4–7 orders higher over the broadband spectral range of 1–25 micrometers. Such ultimate, but potentially tunable mid-IR structured, multi-band absorption of various sulfur-impurity clusters and smooth free-carrier absorption are break through advances in mid-infrared (mid-IR) laser and radiofrequency (RF) hyperthermia-based therapies, as envisioned in the RF-heating tests, and in fabrication of higher-efficiency thin-film and bulk photovoltaic devices with ultra-broad (UV−mid-IR) spectral response.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

Dinuclear gold(I)-N-heterocyclic carbene complexes: Synthesis,characterization, and catalytic application for hydrohydrazidation of terminal alkynes

Dinuclear gold(I)-N-heterocyclic carbene complexes were developed for the hydrohydrazidation of terminal alkynes. The gold(I)-N-heterocyclic carbene complexes 2a-2b were synthesized in good yields from silver complexes synthesized in situ, which in turn were obtained from the corresponding imidazolium salts with Ag₂O in dichloromethane as a solvent. The new air-stable gold(I)-NHC complexes, 2a - 2b, were characterized using NMR spectroscopy, elemental analysis, infrared, and mass spectroscopy studies. The gold(I) complex 2a was characterized using X-ray crystallography. Bis-N-heterocyclic carbene–based gold(I) complexes 2a - 2b exhibited excellent catalytic activities for hydrohydrazidation of terminal alkynes yielding acylhydrazone derivatives. The working catalytic system can be used in gram-scale synthesis. In addition, the catalytic reaction mechanism of the hydrohydrazidation of terminal alkynes by gold(I)-NHC complex was studied in detail using density functional theory.     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Optimization of extraction and quantification technique for phenolics content of garlic (Allium sativum): An application for comparative phytochemical evaluation based on cultivar origin

A range of conventional, i.e. maceration, percolation, ultrasonic assisted, Soxhlet and Soxtec extraction (STE), to advanced extraction techniques of accelerated solvent extraction (ASE) was utilized for the first time in order to optimize the extract yield and recovery of phenolics—gallic acid (GA), rutin (RT) and quercetin (QT)—quantified via ultra-high performance liquid chromatography with diode array detector (UHPLC–DAD). The effect of solvents (n-hexane, dichloromethane and methanol) and temperature (60, 80 and 100°C) upon extraction yield, phenolic content and antioxidant activity (DPPH, ABTS and DPPH) was studied, and the method was validated in commercial food samples from Saudi Arabia, China and India. A high extract yield with percentage recovery was observed for STE (1221.10 mg/5 g; 24.42%) and ASE techniques (91.50 mg/1 g; 9.15%) in methanol at 100°C. UHPLC–DAD showed retention times (min) of 0.67, 1.93 and 1.90 for GA, RT and QT, respectively in the shortest runtime of 3 min. The yield for phenolics was higher for STE/ASE (ppm): 15.27/15.29 (GA), 85.24/37.56 (RT) and 52.20/33.40 (QT), respectively. In terms of antioxidant activities, low IC₅₀ values (μg/ml) of 1.09/1.18 (DPPH), 2.11/5.32 (ABTS) and 4.35/7.88 (phenazine methosulfate–nicotinamide adenine dinucleotide) were observed for STE and ASE, respectively. Multivariate analysis for STE showed a significant (P = 0.000) correlation for extraction type vs. extract yield and phenolics content; however, there was no significance for antioxidant activities vs. extraction type. ASE showed a positive correlation for solvent vs. extraction yield, phenolics and antioxidant activity; however, there was no correlation for extraction yield and DPPH activity. Principal component analysis for STE showed a major variability (52.02%) for extraction yield and phenolics in PC1 followed by PC2 (38.30%) for antioxidant activities. For ASE, PC1 (48.68%) showed a positive correlation for solvent vs. extraction yield and phenolics while PC2 (33.12%) showed a positive correlation for temperature and antioxidant activities. STE and ASE were the optimized extraction techniques for the garlic food sample while a significant effect of solvent and temperature was observed upon extraction yield, phenolics and antioxidant activity.     

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.