Design and coordination behavior of the first selective recognition ligand of 147Pm(III)

A new amide tripodal ligand, 6-[2-(2-diethylamino-2-oxoethoxy)ethyl]-N,N,12-triethyl-11-oxo-3,9-dioxa-6,12-diazatetradecanamide (4) has been designed and synthesized for the recognition of rare earth ions. Three representative complexes of trivalent lighter (La), middle (Gd), and heavier (Er) rare earth ions with 4 were synthesized and characterized by X-ray crystallography. In the complex, the heptadentate forms a cup-like coordination cavity encapsulating the central ion. Different supramolecular complex dimers are constructed by pi-pi interaction and van der Waals forces in accordance with the lanthanide contraction. The differences of the cavity and dimer structures were investigated further by assessing the separation efficiency of in multitrace solvent extraction of rare earth ions from picrate acid solution and the ligand has the best separation factor for 147Pm(III).     

STUDY ON PREPARATION OF INORGANIC COMPOSITE MEMBRANE AND ITS PROPERTIES FOR HYDROGEN PERMEATION

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Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics

In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.     

A comparative study on the structural changes in leucoemeraldine and emeraldine base upon doping by perchlorate

The changes in the structure of leucoemeraldine (LM) and emeraldine (EM) base upon doping by perchlorate anions are studied by X-ray photoelectron spectroscopy (XPS) and infrared (IR) absorption spectroscopy. In the case of LM, interactions of the amine nitrogens with the perchlorate anions result in a nitrogenonium ion structure analogous to that arising from the protonation of imine nitrogens in EM by HCl except the chloride anion in the latter has been replaced by the perchlorate anion. A small amount of partially ionic and covalent chlorine is also incorporated in the LM–perchlorate complexes. The maximum electrical conductivity that is achieved in these complexes is about 4 S/cm. In contrast, the maximum conductivity of the EM–perchlorate complexes is three orders of magnitude lower. The interactions of perchlorate anions with EM base result in the preferential disappearance of the imine units over the amine units.     

An automatic photometric method with high precision by gradually diluting a sample

An automatic photometric method to increase the precision of measurement is proposed, which is based on the injection of a very small volume of sample by rotary valve and the subsequent homogeneous mixing in a small reaction cell made of glass of the sample with a color-developing reagent gradually delivered by a syringe piston pump until the absorbance of the mixture approaches 0.434, where the lowest relative error in the concentration locates. This photometric method is characteristic of uniformly high precision, low sample and reagent consumption, and high sampling rate of 30 samples per h. The other advantages of this method include easy calibration with only one standard solution and no strict requirements on photometric components. While applied for the determination of cobalt ranging from 0.21 to 1.43 g 1(-1), the relative standard deviations are all below 0.4%.     

Can TMS and DSS be used as NMR references for cyclodextrin species in aqueous solution?

Tetramethylsilane (TMS) can be included by -cyclodextrin (-CD), and sodium 2,2-dimethylsilapentane-5-sulphonate (DSS) can form inclusion complexes with - and -CD. The NMR chemical shifts are changed considerably as a result of the strong interaction between CD and the guest compound in the inclusion complexes. A downfield shift of as much as 0.63 ppm shift downfield has been observed for the protons of external TMS in CD aqueous solution. In view of this, the question arises of whether TMS and DSS can be used as internal references. DSS in D₂O is suggested as an external reference for aqueous cyclodextrin solution in NMR measurements.     

Detection of mitochondrial DNA mutations using temporal temperature gradient gel electrophoresis

Mitochondrial disorders are a group of clinically and genetically heterogeneous diseases. Common recurrent mitochondrial DNA (mtDNA) point mutations account for the molecular defects of a small proportion of patients. In order to identify mtDNA mutations, comprehensive mutational analysis of the entire mitochondrial genome is necessary. We developed the temporal temperature gradient gel electrophoresis (TTGE) method to screen for mutations in mtDNA. The entire mitochondrial genome was amplified using 32 pairs of overlapping primers followed by TTGE analysis of the DNA fragments. TTGE method was first validated on 200 DNA fragments containing known mutations or polymorphisms. On TTGE, homoplasmic nucleotide substitutions show a single band shift and heteroplasmic mutations show multiple banding patterns. The known mutations or polymorphisms were correctly identified. TTGE was then used to screen for unknown mutations in the mitochondrial genome. DNA banding patterns, deviated from wild-type, suggestive of either homoplasmic or heteroplasmic mutations, were followed by direct DNA sequencing to identify the mutations. Numerous mutations and polymorphisms were detected. The results demonstrated that TTGE detects and distinguishes heteroplasmic mutations from homoplasmic polymorphisms. It also detects heteroplasmic changes in the background of a homoplasmic polymorphism. Overall, TTGE was proven to be a simple, rapid, sensitive, and effective mutation detection method.     

Biosorption of metal ions with Penicillium chrysogenum

Biosorption of metal ions with Penicillium chrysogenum mycelium is described in this article. Alkaline pretreatment was used to remove proteins and nucleic acids from cells, and this treatment increased the adsorption capacities, for Cr³⁺ from 18.6 mg g⁻¹ to 27.2 mg g⁻¹, for Ni²⁺ from 13.2 mg g⁻¹ to 19.2 mg g⁻¹, for Zn²⁺ from 6.8 mg g⁻¹ to 24.5 mg g⁻¹. The adsorption of metal ions was strongly pH dependent. The mycelium could beused for large-scale removal of Cr³⁺ from tannery wastewater. The results show that this inexpensive mycelium adsorbent has potential in industry because of its high adsorption capacity. The main chelating sites are amino groups (−NH₂) of chitosan in the mycelium. A new model is established, which describes the relation of adsorption of metal ions on pH according to amino group chelating with metal ions and H⁺. The relative errors of simulation for Cu²⁺, Ni²⁺, Zn²⁺, and Cr³⁺ are 4.66%, 5.45%, 11.55%, and 1.69%, respectively.     

Synthesis and characterization of complexes of lanthanide nitrates with N,N′-dinaphthyl-N,N′-diphenyl-3,6-dioxaoctanediamide

Solid complexes of lighter lanthanide nitrates with N,N′-dinaphthyl-N,N′-diphenyl-3,6-dioxaoctanediamide (DDD), Ln(NO₃)₃(DDD) (Ln = La---Nd, Sm) have been prepared in non-aqueous media. These complexes have been characterized by elemental analysis, conductivity measurements, IR spectra, electronic spectra and TG-DTA techniques. In all the complexes, DDD and NO₃⁻ are coordinated to the lanthanide ions as tetradentate and bidentate ligands, respectively. The differences in the IR and electronic spectra between these complexes and lanthanide nitrate complexes with N,N,N′,N′-tetraphenyl-3,6-dioxaoctanediamide (TDD) are discussed.     

Theoretical studies of the geometries of H2GeLiCl and its insertion reaction with R-H (R = F,OH, NH2)

The geometries and insertion reactions of germylene derivative H₂GeLiCl with R-H (R = F, OH, NH₂) have been investigated at the B3LYP/6-311+G^* level of theory. The potential barriers of the three reactions are 93.5, 151.3, and 194.1 kJ/mol, including the zero-point vibration energy corrections, respectively. The mechanisms of all the three reactions are identical, i.e., an intermediate has been located during the insertion reaction. The intermediate could dissociate to substituted germylene and LiCl as a barrier process. Correspondingly, the reaction free energies for the three reactions are −7.4, 49.9, and 64.4 kJ/mol, respectively.