Reactions of platinum complexes with 4,7-phenanthroline: crystal structures of mono- and binuclear platinum(II) complexes containing 4,7-phenanthroline

The reaction of a mixture of cis and trans-[PtCl₂(SMe₂)₂] with 4,7-phen (4,7-phen = 4,7-phenanthroline) in a molar ratio of 1 : 1 or 2 : 1 resulted in the formation of mono and binuclear complexes trans-[PtCl₂(SMe₂)(4,7-phen)] (1) and trans-[Pt₂Cl₄(SMe₂)₂(μ-4,7-phen)] (2), respectively. The products have been fully characterized by elemental analysis, ¹H, ¹³C{¹H}, HHCOSY, HSQC, HMBC, and DEPT-135 NMR spectroscopy. The crystal structure of 1 reveals that platinum has a slightly distorted square planar geometry. Both chlorides are trans with a deviation from linearity 177.66(3)°, while the N–Pt–S angle is 175.53(6)°. Similarly, the reaction of a mixture of cis and trans-[PtBr₂(SMe₂)₂] with 4,7-phen in a 1 : 1 or 2 : 1 mole ratio afforded the mono or binuclear complexes trans-[PtBr₂(SMe₂)(4,7-phen)] (3) and trans-[Pt₂Br₄(SMe₂)₂(μ-4,7-phen)] (4), respectively. The crystal structure of trans-[Pt₂Br₄(SMe₂)₂(μ-4,7-phen)].C₆H₆ reveals that 4,7-phen bridges between two platinum centers in a slightly distorted square planar arrangement of the platinum. In this structure, both bromides are trans, while the PtBr₂(SMe₂) moieties are syn to each other. NMR data of mono and binuclear complexes of platinum 1–4 show that the binuclear complexes exist in solution as a minor product, while the mononuclear complexes are major products.     

Insight into Heterogeneity Effects in Methane Hydrate Dissociation via Pore-Scale Modeling

A large number (1253) of high-quality streaming potential coefficient (\(C_\mathrm{sp})\) measurements have been carried out on Berea, Boise, Fontainebleau, and Lochaline sandstones (the latter two including both detrital and authigenic overgrowth forms), as a function of pore fluid salinity (\(C_\mathrm{f})\) and rock microstructure. All samples were saturated with fully equilibrated aqueous solutions of NaCl (10\(^{-5}\) and 4.5 mol/dm\(^{3})\) upon which accurate measurements of their electrical conductivity and pH were taken. These \(C_\mathrm{sp}\) measurements represent about a fivefold increase in streaming potential data available in the literature, are consistent with the pre-existing 266 measurements, and have lower experimental uncertainties. The \(C_\mathrm{sp}\) measurements follow a pH-sensitive power law behaviour with respect to \(C_\mathrm{f}\) at medium salinities (\(C_\mathrm{sp} =-\,1.44\times 10^{-9} C_\mathrm{f}^{-\,1.127} \), units: V/Pa and mol/dm\(^{3})\) and show the effect of rock microstructure on the low salinity \(C_\mathrm{sp}\) clearly, producing a smaller decrease in \(C_\mathrm{sp}\) per decade reduction in \(C_\mathrm{f}\) for samples with (i) lower porosity, (ii) larger cementation exponents, (iii) smaller grain sizes (and hence pore and pore throat sizes), and (iv) larger surface conduction. The \(C_\mathrm{sp}\) measurements include 313 made at \(C_\mathrm{f} > 1\) mol/dm\(^{3}\), which confirm the limiting high salinity \(C_\mathrm{sp}\) behaviour noted by Vinogradov et al., which has been ascribed to the attainment of maximum charge density in the electrical double layer occurring when the Debye length approximates to the size of the hydrated metal ion. The zeta potential (\(\zeta \)) was calculated from each \(C_\mathrm{sp}\) measurement. It was found that \(\zeta \) is highly sensitive to pH but not sensitive to rock microstructure. It exhibits a pH-dependent logarithmic behaviour with respect to \(C_\mathrm{f}\) at low to medium salinities (\(\zeta =0.01133 \log _{10} \left( {C_\mathrm{f} } \right) +0.003505\), units: V and mol/dm\(^{3})\) and a limiting zeta potential (zeta potential offset) at high salinities of \({\zeta }_\mathrm{o} = -\,17.36\pm 5.11\) mV in the pH range 6–8, which is also pH dependent. The sensitivity of both \(C_\mathrm{sp}\) and \(\zeta \) to pH and of \(C_\mathrm{sp}\) to rock microstructure indicates that \(C_\mathrm{sp}\) and \(\zeta \) measurements can only be interpreted together with accurate and equilibrated measurements of pore fluid conductivity and pH and supporting microstructural and surface conduction measurements for each sample.     

Preparation of new supramolecular liquid-crystalline polyesters containing 3-chloro-4-(alkoxy)benzoic acids

Supramolecular liquid-crystalline polyester complexes based on intermolecular hydrogen bonds between the carboxylic group and the pyridyl moieties was prepared by using non-liquid-crystalline H-donors, [3-chloro-4-(butyloxy)benzoic acid (2a), 3-chloro-4-(octyloxy)benzoic acid (2b), 3-chloro-4-(dodecyloxy)benzoic acid (2c) and 3-chloro-4-(tetradecyloxy)benzoic acid (2d)] and H-acceptor-polyester containing pyridyl units. Intermolecular hydrogen bond formation was confirmed by Fourier transform infrared spectroscopy. The liquid-crystalline behavior of the complex formed was established by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The polyester complexes containing 2c and 2d donor components exhibit liquid crystalline mesophase and behave as side-chain liquid-crystalline polymers. Compared with unsubstituted parent acid, the presence of chloro group as a lateral substituent has a little negative effect on the induction of liquid crystallinity on the polyester complexes systems. The results show that the more stability of the obtained H-bonded complexes in comparison with analogues without 3-Cl substituents is due to the increased acidity of benzoic acid moiety.     

In vitro selection and characterization of deoxyribonucleic acid aptamers for digoxin

The low therapeutic index of digoxin necessitates careful monitoring of its serum levels. Most of digoxin immunoassays suffer from interferences with digoxin-like immunoreactive substances. Since aptamers have been shown to be highly specific for their targets, the aim of this study was to develop DNA aptamers for this widely used cardiac glycoside. Digoxin was coated onto the surface of streptavidin magnetic beads. DNA aptamers against digoxin were designed using Systematic Evolution of Ligands by Exponential enrichment method (SELEX) by 11 iterative rounds of incubation of digoxin-coated streptavidin magnetic beads with synthetic DNA library, DNA elution, electrophoresis and PCR amplification. The PCR product was cloned and sequenced. Binding affinity was determined using digoxin–BSA conjugate, coated onto ELISA plate. Inhibitory effect of anti-digoxin aptamer was conducted using isolated guinea-pig atrium. Three aptamers (D1, D2 and D3) were identified. Binding studies of fluorescein-labeled truncated (without primer binding region) D1 and D2 and full length D1 anti-digoxin aptamers were performed and their corresponding dissociation constants values were 8.2 × 10⁻⁹, 44.0 × 10⁻⁹ and 17.8 × 10⁻⁹ M, respectively. This is comparable to what other workers have obtained for interaction of monoclonal antibodies raised against digoxin. There was little difference in binding affinity between full length and truncated anti-digoxin D1 aptamer. D1 anti-digoxin aptamer also inhibited the effects of digoxin on the isolated guinea-pig atrium. D1 anti-digoxin aptamer distinguished between digoxin and ouabain in both tissue study and binding experiments. Our finding indicated that D1 anti-digoxin aptamer can selectively bind to digoxin. Further studies might show its suitability for use in digoxin assays and as a therapeutic agent in life-threatening digoxin toxicity.     

Genetically Encoded Ratiometric RNA‐Based Sensors for Quantitative Imaging of Small Molecules in Living Cells

Precisely determining the intracellular concentrations of metabolites and signaling molecules is critical in studying cell biology. Fluorogenic RNA‐based sensors have emerged to detect various targets in living cells. However, it is still challenging to apply these genetically encoded sensors to quantify the cellular concentrations and distributions of targets. Herein, using a pair of orthogonal fluorogenic RNA aptamers, DNB and Broccoli, we engineered a modular sensor system to apply the DNB‐to‐Broccoli fluorescence ratio to quantify the cell‐to‐cell variations of target concentrations. These ratiometric sensors can be broadly applied for live‐cell imaging and quantification of metabolites, signaling molecules, and other synthetic compounds.     

Thermotropic polyesters. 2: Synthesis, characterization and thermal transitions of copolyesters containing 4,4′-bis (ω-alkyloxy) biphenyl isophthalate units

Thermotropic copolyesters containing an isophthalate unit and mesogenic 4, 4′-bis (ω-hydroxyalkyloxy) biphenyls (n = 3, 4, 6) with different numbers of methylene units have been synthesized by melt polymerization. The number-average molar mass (M_n) was estimated from end group analysis by ¹H NMR. The copolymer compositions were also obtained from ¹H NMR. The thermal behavior of the copolymers containing even-even (n = 4, 6) and odd-even (n = 3, 4) pairings has been investigated and is also compared with that of the analogous homopolymers. The copolymers exhibit reduced melting point and extending liquid crystalline range identified using polarizing microscopy and DSC. All of the obtained compounds were characterized by conventional spectroscopic methods.     

Effects of graphene quantum dot (GQD) on photoluminescence,mechanical, thermal and shape memory properties of thermoplastic polyurethane nanocomposites

A group of shape memory polyurethane‐based nanocomposites containing graphene quantum dot nanoparticles (GQDs) were prepared via in‐situ polymerization method. GQD nanoparticles were synthesized by a facile and rapid microwave‐assisted method and characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐ray diffraction pattern, field emission scanning microscopy, transmission electron microscopy, and fluorescence analysis. Chemical structure and hydrogen bonding index (HBI_[C=O]) of the nanocomposites were analyzed via FTIR spectra. The results show that the incorporation of GQDs in PU matrix reduces HBI_(C=O) of nanocomposites. Crystalline structure and thermal properties of the nanocomposites were investigated by differential scanning calorimetry. As results indicate, nucleation effect of GQDs raises crystallinity content of the samples. Mechanical examinations indicate that incorporation of GQDs improves Young's modulus of the nanocomposites, while their elongation at break values are reduced. In addition, shape memory analyses reveal that the presence of GQDs in PU matrix increases the shape fixity ratios in nanocomposites.     

Simultaneous spectrophotometric determination of levodopa and carbidopa in pharmaceutical formulations and water samples by using mean centering of ratio spectra and H-point standard addition methods

Two spectrophotometric methods are described for the simultaneous determination of binary mixtures of carbidopa and levodopa in pharmaceutical formulations, without prior separation steps, using the mean centering of ratio spectra and H-point standard addition methods (HPSAM). The methods are based on the difference in the absorption spectra for the products of the reaction of carbidopa and levodopa with 4-aminobenzoic acid in the presence of periodate ion at pH 4.0. The methods allow rapid and accurate determination of carbidopa and levodopa. The results showed that the methods were capable to simultaneous determination of 0.30-10.00 microg ml(-1) and 0.50-10.00 microg ml(-1) each of carbidopa and levodopa. The proposed methods were successfully applied to the simultaneous determination of carbidopa and levodopa in pharmaceutical samples.