Diastereomeric Difference of the Self-Inclusion Complex of N(N′-Formyl-Phenylalanyl)-Deoxyamino-β-Cyclodextrin Caused by the Interaction between the Arm and the Rim of the Cavity

A complete assignment of proton resonances for N(N-formyl d-phenylalanyl)-deoxyamino--cyclodextrin (1d) was performed by means of 1D and 2D NMR,¹H–^1H-COSY, ¹H–^13C-COSY, TOCSYand NOESY spectroscopy. Based on 2D-NMR ROESY and circular dichroism spectroscopy, the conformation of 1d was determined; the phenyl group stays inside the distorted cyclodextrin (CyD) cavity forming a self-inclusion complex, which is almost the same as N(N-formyl l-phenylalanyl)-deoxyamino--CyD (1l). The remarkable diastereomeric difference was observed in the chemical shifts of H(5) and H(6) protons at the narrow rim of the CyD cavity and induced circular dichroism spectra. These results suggest the existence of hydrogen bonds between the hydroxyl group on CyD and the amide groups on the arms, which provides the difference in the molecular recognition properties.     

N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

疏水分配常数用于反相液相色谱保留值的预测

在反相液相色谱保留值基本方程log k_′=a+_cC_B的基础上,描述了采用疏水分配常数及氢键作用能来预测a、c参数的方法,并系统讨论了疏水分配常数对参数a、c的影响,借此对反相液相色谱宽浓度范围内的保留值进行了预测。     

过渡金属络合物成键本质分析的常用方法

过渡金属络合物中过渡金属与配体间所形成的化学键的成键本质,可以在理论化学基础上,采用定量的方法进行分析。本文重点以铁羰基络合物为例,对常用的分析方法,如自然键轨道方法(NBO)、电荷分解分析(CDA)、分子中的原子(AIM)拓扑分析方法以及ETS和EDA能量分解方法等,在应用中的优缺点进行了分析和评述。借助于这些方法提供的电荷、能量和电子密度等配分项可以深刻认识和理解过渡金属-配体间形成的化学键的成键本质。     

Separation behaviors of xylenol isomers by gas chromatography with helps of hydrogen bonding

Summary Xylenol isomers can be resolved on most polyols (sugars or sugar alcohols) and polyethers (polyethylene glycol or polypropylene glycol) with hydrogen-bonding interaction. They are separated on vinical polyols which have more hydroxy hydrogen than tetrol, and even on vicinal triol when its hydroxy hydrogen is acidic (stronger proton donor). The stronger is the hydrogen bonding interaction between xylenols and the liquid phase, the better is the separation of 2,4- and 2,5-xylenol, and the poorer the separation of 2,4-and 2,3-xylenol.     

Crosslinked polystyrene with improved mechanical properties

The synthesis of some divinyl monomers—bis(vinylphenyl)ethane ( 2 ), bis(vinylbenzyloxy)hexane ( 3a ), and bis(vinylbenzyloxy)dodecane ( 3b ) is reported. Copolymers of the new monomers and styrene were evaluated as an alternative to divinylbenzene-crosslinked polymers for use as matrices and absorbents. The mechanical properties and the amount of residual double bonds in the copolymers were compared. It was found that the new copolymers, unlike the divinylbenzene-crosslinked polymers, retained their mechanical strength even at high crosslinking degrees. Stress at break values of 79, 68, and 18 N/mm² were found for the polymers crosslinked with 20 mol % of 3a, 2 , and divinylbenzene; 5, 25 and 45% of the divinyl units in these polymers were left as pendant double bonds. Porous styrene– 2 copolymers were synthesized and shown to have lower surface areas than the corresponding divinylbenzene-crosslinked polymers. The pore size distribution showed that this was due to the absence of the smallest pores which are found in the divinylbenzene-crosslinked polymers in between heavily crosslinked nodules. © 1993 John Wiley & Sons, Inc.     

Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).     

The ion product of H2O,dissociation constants of H2CO3 and pitzer parameters in the system Na+/H+/OH−/HCO 3 − /CO 3 2- /ClO 4 − /H2O at 25°C

The ion product of water and the dissociation constants of carbonic acid have been determined in 0.1, 1.0, 3.0, and 5.0M NaClO₄ at 25°C. The ion product of water K _w ^' has been evaluated by emf measurements with a combined glass electrode in NaClO₄ solutions containing 0.001–0.1M HCLO₄ or NaOH. The product K _H ^' K _l ^' K ₂ ^' of the Henry constant for CO₂ and the dissociation constants for H₂CO₃ have been determined by titration of carbonate solutions equilibrated with pCO₂ =10^–3.52 atm, and K ₂ ^' has been evaluated by potentiometric titration and by measuring the H⁺ concentration at fixed HCO ₃ ^– and CO ₃ ^2- concentrations. The ion interaction (Pitzer) equations are applied to describe the constants K _w ^' , K ₂ ^' and K _H ^' H ₁ ^' K ₂ ^' as a function of the NaClO₄ concentration. The experimental data are used to evaluate the mixing parameters _{i/ClO 4} and _{i/ClO 4} ^-/Na⁺ fori = OH ^-,HCO ₃ ^- andCO ₃ ^2-     

Short Te …︁ Te bonding contacts in a new layered ternary telluride: Synthesis and crystal structure of 2D Nb3GexTe6 (x ≃ 0.9)

The new layered ternary compound Nb₃Ge_xTe₆ (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (R_w = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean d_{Ge? Te} distance (276.5 pm) is in agreement with Ge^II cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe₂ compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs.     

Hydrogen bonded layer-by-layer assembly of poly(2-vinylpyridine) and poly(acrylic acid): Influence of molecular weight on the formation of microporous film by post-base treatment

This article describes the buildup of hydrogen bonded multilayer film of poly(2-vinylpyridine) (P2VP) and poly(acrylic acid) (PAA), and the influence of polymer molecular weight on the formation of microporous film by post-base treatment. The formation of a microporous film involved a two-step mechanism: the release of PAA from P2VP/PAA multilayer, and the reorganization of the remaining P2VP on the substrate. Fourier transform infrared spectroscopy (FT-IR) indicated that the release of PAA from hydrogen bonded multilayer was a rapid process, which was almost independent of the molecular weight of PAA. Furthermore, the molecular weight of P2VP had a great effect on micropore formation by immersing the P2VP/PAA multilayer in basic solution. The rate of micropore formation increased with increasing molecular weight. We anticipate that a comparative study on P2VP/PAA films containing high or low molecular weight polymer provides a way to control the surface morphology, and will be helpful and constructive for the forthcoming discussion about the formation of the microporous film.