Two Unusual Carbohydrate Reactions: Nucleophilic Ring Opening of an Anhydrosugar and Reductive Elimination with Co‐occurring Hydrogenation

Treatment of the 1,6‐anhydrosugar epoxide 5 with a cyano‐Gilman cuprate [(CuCN (6 eq.), MeLi (12 eq.)] surprisingly led to the open chain rearranged (2S,3R)‐1,2‐dihydroxy‐3,6‐dimethylheptan‐4‐one (7), structurally confirmed by conversion to the corresponding diacetate 8. Another unusual reaction was found by hydrogenation of the 2‐tosyl‐1‐bromosugar 11, leading in one operation to the twofold deoxygenated chiral pyran derivative 14. This procedure might prove to be useful in the rapid deoxygenation of sugar derivatives.     

Sol–gel synthesis and characterization of conducting polythiophene/tin phosphate nano tetrapod composite cation-exchanger and its application as Hg(II) selective membrane electrode

Nano tetrapod based on conducting polythiophene (PTh) and tin-phosphate (SnP) were synthesized by in situ chemical oxidative polymerization. The morphology of the resulting polythiophene tinphosphate composite was characterized by elemental analysis, fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The physico-chemical characterization carried out on the composite showed that SnP was modified by conducting PTh with an enhancement of various properties. On the basis of highest distribution coefficient values for Hg(II), the composite was also used for the preparation of Hg(II) selective membrane electrode. The electrode showed working concentration range of 1 × 10^?1 to 1 × 10^?7 with Nernstian slope of 29.29 mV per decade change in concentration and the electrode may be used for wide working pH range of 4–8 having quick response time about 23 s. The life of electrode is 4 months without any notable drift in potential.     

Potentiometric determination of moxifloxacin in some pharmaceutical formulation using PVC membrane sensors

Background

The construction and electrochemical response characteristics of Poly (vinyl chloride) membrane sensors for moxifloxacin HCl (MOX) are described. The sensing membranes incorporate ion association complexes of moxifloxacin cation and sodium tetraphenyl borate (NaTPB) (sensor 1), phosphomolybdic acid (PMA) (sensor 2) or phosphotungstic acid (PTA) (sensor 3) as electroactive materials.

Results

The sensors display a fast, stable and near-Nernstian response over a relative wide moxifloxacin concentration range (1 × 10^-2 - 4.0 × 10^-6, 1 × 10^-2 - 5.0 × 10^-6, 1 × 10^-2 - 5.0 × 10^-6 M), with detection limits of 3 × 10^-6, 4 × 10^-6 and 4.0 × 10^-6 M for sensor 1, 2 and 3, respectively over a pH range of 6.0 - 9.0. The sensors show good discrimination of moxifloxacin from several inorganic and organic compounds. The direct determination of 400 μg/ml of moxifloxacin show an average recovery of 98.5, 99.1 and 98.6% and a mean relative standard deviation of 1.8, 1.6 and 1.8% for sensors 1, 2 and 3 respectively.

Conclusions

The proposed sensors have been applied for direct determination of moxifloxacin in some pharmaceutical preparations. The results obtained by determination of moxifloxacin in tablets using the proposed sensors are comparable favorably with those obtained using the US Pharmacopeia method. The sensors have been used as indicator electrodes for potentiometric titration of moxifloxacin.

     

π‐Excess Aromatic σ2P Ligands: Formation of a Heterocyclic 1,2‐Diphosphine by the Addition of tBuLi and Subsequent Inverse Addition of the Product at the P=C Bonds of Two Molecules of 1‐Neopentyl‐1,3‐benzazaphosphole

The reactivity of tBuLi (pentane) toward the N‐neopentyl‐substituted π‐excess P=CH–N heterocycle 1 depends on the solvent (tetrahydrofuran, diethyl ether, hexane, and toluene) and reaction conditions. Trapping of the resulting organolithium compounds with CO₂/ClSiMe₃, ClSiMe₃, or EtI led to various products indicating CH lithiation ( 1a , b ), normal addition of tBuLi at the P=C bond (E/Z ‐2a , b ), inverse addition of the primary addition product 2_Li at the P=C bond of a second molecule 1 , affording 3‐tert‐butyl‐2,2’‐bis(1,3‐benzazaphospholines) 3 , or inverse addition of tBuLi ( 4b,c ). The formation of 3 demonstrates a novel route to asymmetric heterocyclic 1,2‐diphosphine ligands. The structure elucidation of the new compounds is based on their ³¹P and ¹³C NMR data with conclusive chemical shifts and P–C coupling constants, that of the isolated PH‐functionalized diphosphine 3 on crystal structure analysis.     

Numerical study of dielectrophoresis-modified inertial migration for overlapping sized cell separation

Circulating tumor cells (CTCs) have been proven to have significant prognostic, diagnostic, and clinical values in early-stage cancer detection and treatment. The efficient separation of CTCs from peripheral blood can ensure intact and viable CTCs and can, thus, give proper genetic characterization and drug innovation. In this study, continuous and high-throughput separation of MDA-231 CTCs from overlapping sized white blood cells (WBCs) is achieved by modifying inertial cell focusing with dielectrophoresis (DEP) in a single-stage microfluidic platform by numeric simulation. The DEP is enabled by embedding interdigitated electrodes with alternating field control on a serpentine microchannel to avoid creating two-stage separation. Rather than using the electrokinetic migration of cells which slows down the throughput, the system leverages the inertial microfluidic flow to achieve high-speed continuous separation. The cell migration and cell positioning characteristics are quantified through coupled physics analyses to evaluate the effects of the applied voltages and Reynolds numbers (Re) on the separation performance. The results indicate that the introduction of DEP successfully migrates WBCs away from CTCs and that separation of MDA-231 CTCs from similar sized WBCs at a high Re of 100 can be achieved with a low voltage of magnitude 4 ×10⁶ V/m. Additionally, the viability of MDA-231 CTCs is expected to be sustained after separation due to the short-term DEP exposure. The developed technique could be exploited to design active microchips for high-throughput separation of mixed cell beads despite their significant size overlap, using DEP-modified inertial focusing controlled simply by adjusting the applied external field.     

Magnetite nanoparticle mediated catalytic aquathermolysis of Omani heavy crude oil

The worldwide demand for energy continues to grow and the production of heavy crude is escalating due to shortage of conventional light crude. The transportation of heavy crude oil from the head-well to the refinery is a challenging task due to its high viscosity and low API gravity. Catalytic aquathermolysis is one of the most significant and cost-effective viscosity reduction techniques employed in the up gradation of the crude oil at elevated temperatures and hence to enhance oil extraction process. In this study, catalytic aquathermolysis of Omani heavy crude oil was performed using magnetite nanoparticles (NPs). The NPs were synthesised by reverse co-precipitation method using iron salts in alkaline medium. The synthesised NPs were characterized using Scanning Electron Microscopy (SEM), X-Ray Powder Diffraction (XRD), Energy Dispersive X- Ray analysis (EDX) and Fourier Transform Infrared Spectroscopy (FTIR). The XRD results exhibited a characteristic peak confirming the high purity of iron oxide nanoparticles. The FTIR spectral analysis designated two well-defined peaks corresponding to wave numbers of 500 ?cm^?1 and 630 ?cm^?1, endorses the presence of Fe–O. The catalytic aquathermolysis experiments were carried out in a Parr high temperature-high pressure batch reactor at different experimental conditions. The processing parameters in temperature range of 250 ?°C - 300 ?°C, 0.1% to 0.3% catalyst loading, water to oil ratio of 1:7 to 3:7 with 24–72 ?h of reaction time. The initial pressure in the reactor was maintained at 32 ?bars and the optimization was performed using the Taguchi method to maximize the level of heavy oil. An orthogonal array was employed to analyse the effects of mean response and mean signal-to-noise ratio (S/N) to upgrade the heavy oil. The regression analysis was used to establish a relationship between the viscosity and experimental parameters. The experimental outcomes indicates that the maximum reduction in viscosity occurred at a processing temperature of 300 ?°C, 1:7 ?W/O ratio, 0.1 ?wt% of catalyst concentration and 48 ?h of reaction time. Similarly, the optimum conditions for the reduction in API gravity were obtained at 280 ?°C temperature, 3:7 ?W/O ratio, 0.2 ?wt% of catalyst concentration and a reaction time of 24 ?h.     

Synthesis of attapulgite-MnO2 nanocomposite from manganese complex by ultrasound for hydrogen storage

The research included the synthesis of a new complex of manganese with 3,4,5-tri-methoxybenzoic acid in the presence of triethylamine as a base to which gives the complex with formula [Mn (TMB)₂].2H₂O. This complex was characterized by FTIR, CHN, magnetic susceptibility and thermal analysis. Furthermore, this complex was used as a novel precursor of manganese in preparing the attapulgite-MnO₂ nanocomposite by one-pot addition method using ultrasound. The resulting nanocomposite was characterized by X-ray diffraction and TEM and the results prove that this composite was found as nanochannel of the diameter 45 nm decorated with 26–41 nm of MnO₂ nanoparticles. The attapulgite-MnO₂ nanocomposite was used in the application of hydrogen storage, and the results proved that attapulgite-MnO₂ nanocomposite has the ability to store 3.55 wt% of hydrogen under a pressure of 90 bar and a temperature of 77 K. Furthermore, the measurement demonstrated that increasing the pressure increased the stored hydrogen, implying that the stored gas will be liberated by altering the pressure, implying that the storage will be of the physical kind.     

Synthesis,characterization and antioxidant,antibacterial activity Zn2+, Cu2+, Ni2+ and Co2+, complexes of ligand [2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole]

New metal complexes of (Zn(II), Co(II), Ni(II) and Cu(II)) based on the ligand 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole] were synthesized, whose structures were determined with the different spectroscopic techniques ¹H NMR,¹³C NMR, FT-IR, UV–Visible and by mass spectrometry. The thermal analysis was performed by TG-DTA. The antioxidant activity of the ligand and its complexes was evaluated by DPPH (2,2-diphenyl-1-picrylhydrazyl) method, in comparison with the synthetic antioxidant, ascorbic acid. The results obtained showed that the antioxidant activity of the ligand and its complexes is moderate and that the copper complex has a high activity that exceeds that of ascorbic acid. Antimicrobial activity of the ligand and its metal complexes was studied against two Gram-positive bacteria: Bacillus subtilis ILP1428B, Staphylococcus aureus CIP543154 and two Gram-negative bacteria: Pseudomonas aeruginosa ATCC27653, Escherichia coli CIP5412 (American Type Culture Collection)the activity data show that the metal complexes are more potent than the free ligand.