Dendrimer modified silica gel for anion exchange chromatography: synthesis, characterization and application

The novel grafted silica supports were investigated. The anion exchanger was prepared by chemical modification of a bare silica gel surface. The support was coated with a polymeric moiety formed by condensation polymerization of primary amine with diepoxide. The synthesized copolymer of methylamine (MA) and 1,4-butanedioldiglycidyl ether (BDDE) exhibited a dendrimer structure. The prepared materials were characterized by elemental analysis, FT-IR spectroscopy and solid state (13)C and (29)Si NMR CP-MAS spectroscopy. The porous structure of the adsorbents was investigated using the low temperature nitrogen adsorption (LTNA) method. It allows determination of the influence of the topology of packing materials on their chromatographic properties. Imaging was also carried out on the surfaces of the synthesized materials by scanning electron microscopy (SEM). The obtained stationary phase was applied in ion chromatography for the separation of inorganic anions (F(-), Cl(-), NO(2)(-), Br(-), NO(3)(-), HPO(4)(2-), SO(4)(2-), ClO(4)(-)). Bicarbonate buffer was used as a mobile phase.     

Effect of End-Capping and Surface Coverage on the Mechanism of Solvent Adsorption

Adsorption of acetonitrile and methanol was measured on non-endcapped and endcapped octadecyl stationary phases. The results enabled us to characterize the effect of end-capping on the adsorption of the organic modifiers. Our results clearly demonstrate how the end-capping groups modify the chromatographic properties of adsorbents. Differences between solvent adsorption mechanisms are also discussed. Adsorption of acetonitrile is governed by hydrophobic effects whereas methanol is adsorbed by the organic ligand by a hydrophobic interaction and by the residual silanols by hydrogen-bond formation and dipole–dipole interactions.     

Zeta potential determination as a new way of stationary phases characterization for liquid chromatography

A set of seven homemade octadecyl silica‐based bonded phases was investigated. Their zeta potential data in methanol and ACN as well as in methanol–water and ACN–water solution were obtained using Zetasizer. The influence of both the coverage density of bonded ligands and the end‐capping of the modified surface on these data was investigated. Presented results may give useful information about the accessibility of the residual silanols in different mobile phases during the chromatographic analysis. Those measurements may be useful to choose chemically bonded stationary phases for CEC. The results also confirm the phenomena of anion exclusion from the pores of stationary‐bonded phase.     

Retention mechanism of the multifunctional solute on columns with different coverage densities using highly aqueous reversed‐phase conditions

A series of 11 homemade octadecyl bonded phases with different coverage densities were tested to determine the influence of the stationary phase on the retention in highly aqueous mobile phases. The concentrations of the organic modifiers (methanol and ACN) were in the range of 0–20%_v/v. The coverage density of bonded ligands and the presence of the end‐capping have strong influence on the solute retention. Amoxicillin (AMO) was chosen as the test compound. Dual properties of AMO, which contain hydrophobic skeleton and polar groups (amino, hydroxyl and carbonyl), cause irregular changes of the retention over the stationary phase hydrophobicity and silanol activity at given mobile phase composition. Presented data show that application of non‐standard low coverage density C18 phases allow to determine AMO in the RPLC condition with high retention.     

Evaluation of Blind Source Separation for different algorithms based on second order statistics and different spatial configurations of directional microphones

The present study is concerned with the convolutive Blind Source Separation (BSS) of sound sources that leads to a significant speech intelligibility enhancement. Two experiments were conducted. In the first experiment two different algorithms of convolutive BSS were compared. Both methods are based on second order statistics since such approach is simple and gives satisfactory performance. The data resulted from this experiment suggested that with different approaches, different speech intelligibility improvement could be obtained. In the second experiment the influence of the spatial configuration of the cardioid microphones on the BSS performance was measured. It was revealed that the best separation for a considered spatial configuration can be obtained when microphones are directed alternately.     

Dichotomies for Lorentz spaces

Assume that L ^p,q , $L^{p_1 ,q_1 } ,...,L^{p_n ,q_n } $ are Lorentz spaces. This article studies the question: what is the size of the set $E = \{ (f_1 ,...,f_n ) \in L^{p_{1,} q_1 } \times \cdots \times L^{p_n ,q_n } :f_1 \cdots f_n \in L^{p,q} \} $ . We prove the following dichotomy: either $E = L^{p_1 ,q_1 } \times \cdots \times L^{p_n ,q_n } $ or E is σ-porous in $L^{p_1 ,q_1 } \times \cdots \times L^{p_n ,q_n } $ , provided 1/p ≠ 1/p ₁ + … + 1/p _n . In general case we obtain that either $E = L^{p_1 ,q_1 } \times \cdots \times L^{p_n ,q_n } $ or E is meager. This is a generalization of the results for classical L ^p spaces.     

Thermal characteristics and analysis of pyrolysis effects during the mechanical alloying process of Astaloy CrM powders

Mechanical alloying processes are carried out usually with addition of some lubricants, referred to also as a process control agents (PCA). About 1–2 wt% of a PCA (usually stearic acid) is normally added to prevent excessive cold welding amongst the powder particles, especially when powders of ductile metals are milled. However, lubricants (maybe disintegrated after MA process) must be removed in the early stages of heating during the sintering process. The aim of the present study was to determine the effect of the MA process especially (i) milling time and (ii) influence of lubricant addition on thermal effects during heating of iron powder (Astaloy CrM) with the addition of 1 wt% stearic acid measured by differential scanning calorimeter (DSC) and thermogravimetry (TG) techniques. Removal of the lubricants during heating of the blended powders and exhaust gases from the furnace were monitored by quadruple mass spectrometry (QMS). Determination of the physical and technological properties of the powder mixture obtained from MA was performed with a laser particle sizer. Distribution of particle sizes, flow and apparent density were also measured. Furthermore, the shape and morphology of the powders were characterised by a light optical microscope (LOM) and scanning electron microscope (SEM).     

Multifunctionality in Bimetallic LnIII[WV(CN)8]3− (Ln=Gd,Nd) Coordination Helices: Optical Activity,Luminescence, and Magnetic Coupling

Two chiral luminescent derivatives of pyridine bis(oxazoline) (Pybox), (SS/RR)‐iPr‐Pybox (2,6‐bis[4‐isopropyl‐2‐oxazolin‐2‐yl]pyridine) and (SRSR/RSRS)‐Ind‐Pybox (2,6‐bis[8H‐indeno[1,2‐d]oxazolin‐2‐yl]pyridine), have been combined with lanthanide ions (Gd³⁺, Nd³⁺) and octacyanotungstate(V) metalloligand to afford a remarkable series of eight bimetallic CN^?‐bridged coordination chains: {[Ln^III(SS/RR‐iPr‐Pybox)(dmf)₄]₃[W^V(CN)₈]₃}_n ? dmf ? 4 H₂O (Ln=Gd, 1 ‐SS and 1 ‐RR; Ln=Nd, 2 ‐SS and 2 ‐RR) and {[Ln^III(SRSR/RSRS‐Ind‐Pybox)(dmf)₄][W^V(CN)₈]}_n ? 5 MeCN ? 4 MeOH (Ln=Gd, 3 ‐SRSR and 3 ‐RSRS; Ln=Nd, 4 ‐SRSR and 4 ‐RSRS). These materials display enantiopure structural helicity, which results in strong optical activity in the range 200–450 nm, as confirmed by natural circular dichroism (NCD) spectra and the corresponding UV/Vis absorption spectra. Under irradiation with UV light, the Gd^III‐W^V chains show dominant ligand‐based red phosphorescence, with λ_max≈660 nm for 1 ‐(SS/RR) and 680 nm for 3 ‐(SRSR/RSRS). The Nd^III‐W^V chains, 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS), exhibit near‐infrared luminescence with sharp lines at 986, 1066, and 1340 nm derived from intra‐f ⁴F_3/2→⁴I_{9/2,11/2,13/2} transitions of the Nd^III centers. This emission is realized through efficient ligand‐to‐metal energy transfer from the Pybox derivative to the lanthanide ion. Due to the presence of paramagnetic lanthanide(III) and [W^V(CN)₈]^3? moieties connected by cyanide bridges, 1 ‐(SS/RR) and 3 ‐(SRSR/RSRS) are ferrimagnetic spin chains originating from antiferromagnetic coupling between Gd^III (S_Gd=7/2) and W^V (S_W=1/2) centers with J _{1 ‐(SS)}=?0.96(1) cm^?1, J _{1 ‐(RR)}=?0.95(1) cm^?1, J _{3 ‐(SRSR)}=?0.91(1) cm^?1, and J _{3 ‐(RSRS)}=?0.94(1) cm^?1. 2 ‐(SS/RR) and 4 ‐(SRSR/RSRS) display ferromagnetic coupling within their Nd^III‐NC‐W^V linkages.