Characterization of calixarene‐bonded stationary phases

Calixarene‐bonded stationary phases received growing interest in HPLC as stationary phases with special retention characteristics and selectivity. The commercially available unsubstituted and p‐tert‐butyl‐substituted Caltrex^® columns have been intensively studied and characterized in our workgroup. They can be used as reversed phases, yet they support additional interactions. Especially, their steric, polar and ionic properties differ from conventional alkyl‐bonded phases. However, also the hydrophobic interaction shows differences since adsorption and partition interactions on or in a bonded layer of calixarenes are not similar to those of alkyl‐bonded layers. The relative strength of the hydrophobic properties of the stationary phases has been found depending on the methanol concentration of the mobile phase. Generally, the dependencies of their interaction strengths on mobile‐phase conditions, e.g. the change of the intensity of the hydrogen‐bonding abilities with decreasing methanol content, are not similar from phase to phase either. This probably gives calixarene‐bonded stationary phases enhanced suitability for analyses at extreme compositions of the mobile phase. An overview about the synthesis, retention and selectivity properties of Caltrex^® columns is given here.     

Functionalization of MWNTs with Hyperbranched PEI for Highly Selective Isolation of BSA

Cationic hyperbranched BPEI was immobilized on the surface of MWNTs via electrostatic interactions between the positively charged protonated amines within the polymer and the carboxyl groups on the chemically oxidized MWNT surface. The functionalized BPEI‐MWNTs were characterized by FT‐IR, TGA, TEM and surface charge analysis, and it was used as a bio‐sorbent for the adsorption of proteins. CD spectra showed no conformational change of BSA during the adsorption/desorption process. A dynamic adsorption capacity of 167 mg · g^?1 for BSA was achieved. With a sample volume of 2.0 mL, an enrichment factor of 10 was obtained along with an adsorption efficiency of 100%, a recovery of 100%, a sampling frequency of 10 h^?1 and a RSD of 2.6% at 25 µg · mL^?1 BSA.

     

AT‐Specific DNA Binding of Binuclear Ruthenium Complexes at the Border of Threading Intercalation

The binuclear ruthenium complex [μ‐bidppz(phen)₄Ru₂]⁴⁺ has been extensively studied since the discovery of its unusual threading intercalation interaction with DNA, a binding mode with extremely slow binding and dissociation kinetics. The complex has been shown to be selective towards long stretches of alternating AT base pairs, which makes it interesting, for example, as a model compound for anti‐malaria drugs due to the high AT content of the genome of the malaria parasite P. falciparum. We have investigated the effect of bridging ligand structure on threading intercalation ability and found that length and rigidity as well as the size of the intercalated ring system are all factors that affect the rate and selectivity of the threading intercalation. In particular, we discovered a new DNA‐threading compound, [μ‐dppzip(phen)₄Ru₂]⁴⁺, which appears to be just at the border of being capable of threading intercalation and displays even greater selectivity for AT‐DNA than the parent compound, [μ‐bidppz(phen)₄Ru₂]⁴⁺.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².     

Hydride vapor phase epitaxy of GaN boules using high growth rates

The boule-like growth of GaN in a vertical AIXTRON HVPE reactor was studied. Extrinsic factors like properties of the starting substrate and fundamental growth parameters especially the vapor gas composition at the surface have crucial impact on the formation of inverse pyramidal defects. The partial pressure of GaCl strongly affects defect formation, in-plane strain, and crystalline quality. Optimized growth conditions resulted in growth rates of 300–500 μm/h. GaN layers with thicknesses of 2.6 and of 5.8 mm were grown at rates above 300 μm/h. The threading dislocation density reduces with an inverse proportionality to the GaN layer thickness. Thus, it is demonstrated that growth rates above 300 μm/h are promising for GaN boule growth.     

ADSORPTION SELECTIVITY FOR Cu~(2 ),Ni~(2 ),Co~(2 )IONS USING CROSSLINKING CHITOSAN RESINS IMPRINTED BY METAL IONS

1introductionChitosan,adeacetylatedderivativeofchitin,isnatUralpolysaccharideswithfreeaminogroups.Itcanactasanexcellentadsorbenttoadsorbnotonlyvariousorganiccompoundsincludingpolychlorinatedbiphenyls,proteinsandnucleicacids,butalsometalions[1~sl.ChitosanhasbeenwidelyemployedasaneffectivecoagulatingagentinactivatedsludgeplantSandfoodprocessingfactories,andalsoinpreparation,concentTationandpurificationofmetalionsinhydrometallurgy.Chitosanbehavesasanaturalchelatingpolymer.Chitosanundergoeschela…     

Synthesis and X-ray analysis of (RS)-N-tert-butyl-2-anilino-

The crystal and molecular structure of (RS)-N-Tert-butyl-2-anilino-3,3-dimethylbutanamide, a derivative of an amino acid that was obtained by highly selective cleavage of 1,3-di-tert-butylaziridinone by aniline, is described. The racemic mixture of the amide crystallizes in the space groupP 2₁/n with four molecules per unit cell. Crystal Data:a=10.483(2) Å,b=6.206(1) Å,c=24.767(5) Å,β=90.39(3),V=1611.5(6) A³,R(F)[I>2σ(I)]=0.0679.wR(F ²) [I>2σ(I)]=0.1148.     

Conditions for the Selective Conversion of Quaternary 3-Anilino-1,5-dimethylpyrazolium Salts into 3-Anilino-1,5-dimethylpyrazole

The possibility has been studied of converting quaternary 3-anilino-1,5-dimethylpyrazolium salts into 3-anilino-1,5-dimethylpyrazole, the first representative of the 1-alkyl-3-arylaminopyrazoles. The dependence of the reaction direction on the nature of the substituent at position 2 has been clarified. The most effective result was obtained with a cyanoethyl substituent. On boiling the initial salt with aqueous ammonia the target product is isolated in quantitative yield. Syntheses of the initial salts are described. C-Sulfonation was detected on interacting 3-anilino-1-benzoyl-3-methylpyrazole and dimethyl sulfate, with the formation of p-(3-amino-1,2,5-trimethylpyrazolio)benzenesulfonate.     

Optical resolution of racemic amino acid derivatives with molecularly imprinted membranes bearing oligopeptide tweezers

Molecularly imprinted polymeric membranes were prepared from various oligopeptide tweezers by the adoption of N‐α‐tert‐butoxycarbonyl‐D ‐tryptophan (Boc‐D ‐Trp) or N‐α‐tert‐butoxycarbonyl‐L ‐tryptophan (Boc‐L ‐Trp) as a print molecule. The chiral recognition ability of the formed molecular recognition sites was dependent on the absolute configuration of the print molecule adopted in the membrane preparation (molecular imprinting) process, whereas the candidate oligopeptide tweezers consisted of the L ‐amino acid residues. In other words, the membranes imprinted by the D ‐isomer recognized the D ‐isomer in preference to the corresponding L ‐isomer, and vice versa. The affinity constant between the target molecule and the chiral recognition site from the oligopeptide tweezers was higher than that from a single‐strand oligopeptide derivative. Those membranes selectively transported the enantiomer, which was preferentially incorporated into the membrane by dialysis. The permselectivities for these membranes exceeded their adsorption selectivities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 385–396, 2005