Copolymer-grafted silica phase from a cation–anion monomer pair for enhanced separation in reversed-phase liquid chromatography

This work reports a new imidazolium and l-alanine derived copolymer-grafted silica stationary phase for ready separation of complex isomers using high-performance liquid chromatography (HPLC). For this purpose, 1-allyl-3-octadecylimidazolium bromide ([AyImC₁₈]Br) and N-acryloyl-l-alanine sodium salt ([AAL]Na) ionic liquids (IL) monomers were synthesized. Subsequently, the bromide counteranion was exchanged with the 2-(acrylamido)propanoate organic counteranion by reacting the [AyImC₁₈]Br with excess [AAL]Na in water. The obtained IL cation–anion monomer pair was then copolymerized on mercaptopropyl-modified silica (Sil-MPS) via a surface-initiated radical chain-transfer reaction. The selective retention behaviors of polycyclic aromatic hydrocarbons (PAHs), including some positional isomers, steroids, and nucleobases were investigated using the newly obtained Sil-poly(ImC₁₈-AAL), and octadecyl silylated silica (ODS) was used as the reference column. Interesting results were obtained for the separation of PAHs, steroids, and nucleobases with the new organic phase. The results showed that the Sil-poly(ImC₁₈-AAL) presented multiple noncovalent interactions, including hydrophobic, π–π, carbonyl–π, and ion–dipole interactions for the separation of PAHs and dipolar compounds. Only pure water was sufficient as the mobile phase for the separation of the nucleobases. Ten nucleosides and bases were separated, using only water as the mobile phase, within a very short time using the Sil-poly(ImC₁₈-AAL), which is otherwise difficult to achieve using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions are important for the effective separation of such basic compounds without the use of any organic additive as the eluent on the Sil-poly(ImC₁₈-AAL) column.

Synthesis and reactions of optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl-(o-methoxyphenyl)phosphine-borane

Cyclohexyl(o-methoxyphenyl)menthyloxyphosphineborane and t-butyl(o-methoxyphenyl)menthyloxyphosphine-borane were prepared from dichlorocyclohexylphosphine and t-butyldichlorophosphine by successive treatments with (−)-menthol, o-methoxyphenylmagnesium bromide, and borane-THF complex. The separated pure diastereomers of each of the compounds underwent reaction with lithium naphthalenide to afford optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl(o-methoxyphenyl)phosphine-borane, respectively. These secondary phosphine-boranes reacted readily with various electrophiles in the presence of bases with virtually net retention of configuration. A new chiral phosphine ligand, (S,S)-1,2-bis[cyclohexyl(o-methoxyphenyl)phosphino]ethane was synthesized via the optically pure phosphine-boranes.     

The synthesis and thermal property of sodium cyclo-octaphosphate

Sodium cyclo-octaphosphate heptahydrate, (NaPO₃)₈ · 7H₂O, has been made by heating lead cyclo-tetraphosphate at 340°C, dissolving the thermal product in a 3% aqueous solution of tetrasodium ethylene-diaminetetraacetate, and then crystallizing it by addition of sodium chloride and acetone to the solution. When the cyclo-octaphosphate was heated up to 400°C, it decomposed to produce phosphates with both shorter and longer chain lengths. A main product at 300° to 350°C was sodium cyclo-triphosphate, and the thermal product melted at about 630°C.     

Fluorescence studies on volume phase transition in poly(acrylamide) and poly(N-isopropylacrylamide) gels

The changes in microenvironments during the volume phase transition of poly(acrylamide) and poly(N-isopropylacrylamide) gels induced by pH change or the change in solvent composition were studied by using dansyl or pyrenyl fluorescent probes.     

Heteroarylthiomethylsilanes. Synthesis and application to heteroarylthiomethylation of carbonyl compounds [1]

Heteroarylthiomethyltrimethylsilanes bearing a 2-pyridyl, 2-imidazolyl, 5-tetrazolyl, or 2-pyrimidinyl group, readily prepared by the reaction of heteroarylmercaptans with halomethyltrimethylsilane in the presence of a base, are synthetic equivalents of heteroarylthiomethyl anions, otherwise inaccessible, and are effective reagents for the introduction of a heteroarythiomethyl group at a carbonyl carbon atom in the presence of a catalytic amount of tetrabutylammonium fluoride.     

Structural and magnetic ordering in the VxNb1+yS2 system

The influence of composition on the structural ordering and magnetism in the V_xNb_1+yS₂ system has been investigated by X-ray diffraction and magnetic measurements. Stoichiometric V_1/3NbS₂ did not exhibit the structural ordering of vanadium between the NbS₂ layers. In the ordered structure, the vanadium composition deviated from the ideal value of to both higher and lower values, while the niobium composition was in the range of 0.05?y?0.18. Excess niobium, y>0, is thought to play an essential role in the structural ordering in this system. For samples with excess niobium and ordered structures, a magnetic transition was observed at 20-50 K, depending on the composition. The spontaneous magnetization of 3-5×10⁻³ μ_B/V atom is thought to be intrinsic to this system. The magnetization curves consisted of a constant and a proportional parts of the magnetic field, which correspond to the spontaneous magnetization and high-field susceptibility, respectively. The magnetization curves and the temperature dependencies of the high-field susceptibility were quite similar to those of the canted antiferromagnetic NiS₂. A correlation between the structural and magnetic ordering is suggested.     

X-ray Crystallographic Observation of Chiral Transformations within a Metal–Peptide Pore

Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation.     

An Alumanylyttrium Complex with an Absorption due to a Transition from the Al−Y Bond to an Unoccupied d-Orbital

The reaction between a dialkyl-substituted alumanyl anion and [Y(CH₂SiMe₃)₂(thf)₃][BPh₄] resulted in the formation of (dialkylalumanyl)yttrium complex 2 , which exhibits the first 2-center–2-electron (2 c-2 e) Al−Y bond. The ¹H and ¹³C NMR spectra of 2 together with an X-ray crystallographic analysis indicated a C_2v symmetrical structure. DFT calculations on 2 revealed that its LUMO consists of overlapping 3 p- and 4 d-orbitals of the Al and Y atoms, respectively, and that the HOMO–LUMO gap is narrow. The UV/Vis spectrum of 2 exhibited a visible absorption at 432 nm, which suggests that the strong σ-donating and π-accepting character of the three-coordinate dialkylalumanyl ligand generates a colored d⁰-complex that does not contain any π-electrons.     

Zeros of Airy Function and Relaxation Process

One-dimensional system of Brownian motions called Dyson’s model is the particle system with long-range repulsive forces acting between any pair of particles, where the strength of force is β/2 times the inverse of particle distance. When β=2, it is realized as the Brownian motions in one dimension conditioned never to collide with each other. For any initial configuration, it is proved that Dyson’s model with β=2 and N particles, $\mbox {\boldmath $\mbox {\boldmath , is determinantal in the sense that any multitime correlation function is given by a determinant with a continuous kernel. The Airy function (z){\rm Ai}(z) is an entire function with zeros all located on the negative part of the real axis ℝ. We consider Dyson’s model with β=2 starting from the first N zeros of Ai(z){\rm Ai}(z) , 0>a ₁>⋅⋅⋅>a _N , N≥2. In order to properly control the effect of such initial confinement of particles in the negative region of ℝ, we put the drift term to each Brownian motion, which increases in time as a parabolic function: Y _j (t)=X _j (t)+t ²/4+{d ₁+∑ _ℓ=1 ^N (1/a _ℓ )}t,1≤j≤N, where d₁=Ai￠(0)/Ai(0)d_{1}={\rm Ai}'(0)/{\rm Ai}(0) . We show that, as the N→∞ limit of $\mbox {\boldmath $\mbox {\boldmath , we obtain an infinite particle system, which is the relaxation process from the configuration, in which every zero of (z){\rm Ai}(z) on the negative ℝ is occupied by one particle, to the stationary state m_Ai\mu_{{\rm Ai}} . The stationary state m_Ai\mu_{{\rm Ai}} is the determinantal point process with the Airy kernel, which is spatially inhomogeneous on ℝ and in which the Tracy-Widom distribution describes the rightmost particle position.