Stability toward alkaline hydrolysis of B. mori silk fibroin grafted with methacrylamide

Bombyx mori silk fibroin fibers were grafted with methacrylamide (MAA) and characterized by Raman and infrared (IR) vibrational spectroscopy before and after hydrolysis in NaOH 5% to elucidate the possible interactions between the two components and the stability of the fibers toward alkaline hydrolysis. Upon grafting, the fibers underwent conformational rearrangements toward a more unordered state and lost orientation at weight gains higher than 60%. Vibrational spectroscopy disclosed the occurrence of intermolecular interactions (mainly hydrogen bonds) between B. mori silk fibroin and polyMAA in the grafted fibers, and the formation of covalent bonds has been explored. These strong interactions made the grafted fibers as a whole more stable toward alkaline hydrolysis because they prevented the solubilization of the polymer upon hydrolysis and made slower the transformation of its CONH₂ groups into COOH and COO⁻ groups. Upon hydrolysis, silk fibroin underwent an enrichment in the β‐sheet crystalline domains, because of the preferential removal of the unordered domains, which were more prone to the OH⁻ attack. IR and Raman spectroscopy proved valid techniques to investigate the degradation mechanism and kinetics of grafted silk fibroin fibers and so for designing high‐performing silk‐based materials. The A₇₃₁/A₁₀₀₄ Raman intensity ratio was proposed to spectroscopically evaluate the composition of the grafted samples; its value was found to linearly increase with weight gain (R² = 0.998), envisaging the possibility of using Raman spectroscopy as a routine analytical technique for qualitative and quantitative characterization of grafted industrial samples. Copyright © 2016 John Wiley & Sons, Ltd.     

Affinity of protein fibres towards sulfation

Wool, Bombyx mori and Antheraea pernyi (Tussah) silk fibres were treated with chlorosulfonic acid in pyridine and investigated by FT‐IR and FT‐Raman spectroscopies as well as mechanical measurements. The reactivity towards sulfation was found to decrease along the series: wool > Bombyx mori silk fibroin > Tussah silk fibroin, in agreement with weight gain which decreased along the same series. Accordingly, Tussah silk maintained its intrinsic tensile properties essentially unchanged upon the treatment, while for Bombyx mori silk fibroin, the tensile performance decreased sharply especially at longer reaction times. Sulfated wool was characterized by an increased fibre extensibility. New IR and Raman bands attributable to various vibrations of sulfated groups were detected in sulfated wool and to a lower extent in Bombyx mori silk fibroin fibres; all the fibres underwent conformational rearrangements upon sulfation, independent of the sulfation yield. Wool fibres treated with chlorosulfonic acid in pyridine bound considerable amounts of sulfate mainly through the hydroxyl groups of serine, threonine and tyrosine. Also, tryptophan and basic amino acids were found to participate to the reaction. B. mori silk fibroin fibres appeared to bind a minor amount of sulfate groups mainly trough the hydroxyl groups of Ser. Weight gain, spectroscopic and mechanical data are discussed in relation to the difference in fibre morphology, structure and crystallinity, as well as to the amount and accessibility of potentially reactive amino acids. Copyright © 2012 John Wiley & Sons, Ltd.     

Kinetics study of a Diels‐Alder reaction in mixtures of an ionic liquid with molecular solvents

The second‐order rate constants for cycloaddition reaction of cyclopentadiene with naphthoquinone were determined spectrophotometrically in various compositions of 1‐(1‐butyl)‐3‐methylimidazolium terafluoroborate ([bmim]BF₄) with water and methanol at 25 °C. Rate constants of the reaction in pure solvents are in the order of water > [bmim]BF₄ > methanol. Rate constants of the reaction decrease sharply with mole fraction of the ionic liquid in aqueous solutions and increase slightly to a maximum in alcoholic mixtures. Multi‐parameter correlation of logk₂ versus solute–solvent interaction parameters demonstrated that solvophobicity parameter (Sp), hydrogen‐bond donor acidity (α) and hydrogen‐bond acceptor basicity (β) of media are the main factors influencing the reaction rate constant. The proposed three‐parameter model shows that the reaction rate constant increases with Sp, α and β parameters. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and surface enhanced Raman scattering of a black dyed silk

The Raman and surface enhanced Raman scattering (SERS) spectra of a black dyed silk sample (BDS) were registered. The spectral analysis was performed on the basis of Raman and SERS spectral data of isolated samples of Bombyx mori silk fibroin, its motif peptide component (GAGAGS) and the synthetic reactive black 5 dye (RB5). The macro FT‐Raman spectrum of the silk sample is consistent with a silk II‐Cp crystalline fraction of Bombyx mori silk fibroin; the SERS spectrum is highly consistent with conformational modifications of the fibroin due to the interactions with the Ag nanoparticles. The GAGAGS peptide sequence dominates the Raman spectrum of the silk. The SERS spectrum of the peptide suggests a random coil conformation imposed by the surface interaction; the serine residue in the new conformation is exposed to the surface. Quantum chemical calculations for a model of the GAGAGS–Ag surface predict a nearly extended conformation at the Ag surface. The Raman spectrum of the dye was analysed, and a complete band assignment was proposed; it was not possible to propose a preferential orientation or organization of the molecule on the metal surface. Quantum chemical calculations for a model of the dye interacting with a silver surface predict a rather coplanar orientation of the RB5 on the Ag metal surface. The Raman spectrum of the BDS sample is dominated by signals from the dye; the general spectral behaviour indicates that the dye mainly interacts with the silk through the sulphone (–SO₂–) and sulphonate (–SO₂–O–) groups. Besides the presence of dye signals, mainly ascribed to the sulphone and sulphonate bands, the SERS spectrum of the BDS sample also displays bands belonging to the amino acids alanine, glycine, serine and particularly tyrosine. Copyright © 2013 John Wiley & Sons, Ltd.     

磁共振技术在丝素蛋白结构与功能研究中的应用

丝素蛋白纤维因其优异的力学性能和良好的生物相容性而得到广泛关注. 人们通过对丝素蛋白二级结构的构象转变及其诱导因素的研究,试图阐明蚕吐丝机理、相关蛋白结构与功能的关系,为人工合成性能优良的丝纤维材料以及认识生命过程提供有益指导和帮助. 磁共振技术是研究丝素蛋白结构最有效的方法之一. 我们课题组多年来运用核磁共振（NMR）的方法研究了桑蚕丝素蛋白的构象及环境对其的影响因素,如pH、金属离子（K⁺、Na⁺、Ca²⁺、Cu²⁺、Zn²⁺）等,并运用电子自旋顺磁共振（EPR）方法研究了金属Cu²⁺离子与丝素蛋白的相互作用,试图揭示蛋白质构象转变与金属离子影响的内在联系. 另外,我们还发展了一种广义二维核磁共振相关技术,有效缩短了传统二维核磁共振的实验时间. 本文将综述这些年来我们所做的相关工作.     

Nature of the transient species formed in the pulse radiolysis of 4‐hydroxybenzyl alcohol in aqueous solutions: observation of equilibrium in the reaction of OH‐adducts with HPO ions

Reactions of ^. OH/O ^.? radicals, H‐atoms as well as specific oxidants such as N and Cl radicals with 4‐hydroxybenzyl alcohol (4‐HBA) in aqueous solutions have been investigated at various pH values using the pulse radiolysis technique. At pH 6.8, ^. OH radicals were found to react with 4‐HBA (k = 6 × 10⁹ dm³ mol^?1 s^?1) mainly by contributing to the phenyl moiety and to a minor extent by H‐abstraction from the ? CH₂OH group. ^. OH radical adduct species of 4‐HBA, i.e., ^. OH‐(4‐HBA) formed in the addition reaction were found to undergo dehydration to give phenoxyl radicals of 4‐HBA. Decay rate of the adduct species was found to vary with pH. At pH 6.8, decay was very much dependent on phosphate buffer ion concentrations. Formation rate of phenoxyl radicals was found to increase with phosphate buffer ion concentration and reached a plateau value of 1.6 × 10⁵ s^?1 at a concentration of 0.04 mol dm^?3 of each buffering ion. It was also seen that ^. OH‐(4‐HBA) adduct species react with HPO ions with a rate constant of 3.7 × 10⁷ dm³ mol^?1 s^?1 and there was no such reaction with H₂PO ions. However, the rate of reaction of ^. OH‐(4‐HBA) adduct species with HPO ions decreased on adding KH₂PO₄ to the solution containing a fixed concentration of Na₂HPO₄ which indicated an equilibrium in the H⁺ removal from ^. OH‐(4‐HBA) adduct species in the presence of phosphate ions. In the acidic region, the ^. OH‐(4‐HBA) adduct species were found to react with H⁺ ions with a rate constant of 2.5 × 10⁷ dm³ mol^?1 s^?1. At pH 1, in the reaction of ^. OH radicals with 4‐HBA (k = 8.8 × 10⁹ dm³ mol^?1 s^?1), the spectrum of the transient species formed was similar to that of phenoxyl radicals formed in the reaction of Cl radicals with 4‐HBA at pH 1 (k = 2.3 × 10⁸ dm³ mol^?1 s^?1) showing that ^. OH radicals quantitatively bring about one electron oxidation of 4‐HBA. Reaction of ^. OH/O ^.? radicals with 4‐HBA by H‐abstraction mechanism at neutral and alkaline pH values gave reducing radicals and the proportion of the same was determined by following the extent of electron transfer to methyl viologen. H‐atom abstraction is the major pathway in the reaction of O ^.? radicals with 4‐HBA compared to the reaction of ^. OH radicals with 4‐HBA. At pH 1, transient species formed in the reactions of H‐atoms with 4‐HBA (k = 2.1 × 10⁹ dm³ mol^?1 s^?1) were found to transfer electrons to methyl viologen quantitatively. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm² for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.     

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl₂, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35–125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, ¹³C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain–chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk fibroin in aqueous solution. It is possible that the silk protein nanoparticles are potentially useful in biomaterials such as cosmetics, anti-UV skincare products, industrial materials and surface improving materials, especially in enzyme/drug delivery system as vehicle.     

Solid phase synthesis of novel α/β‐tetrapeptides,electrospray ionization mass spectrometric evaluation of their metal cation complexation behavior,and conformational analysis using density functional theory (DFT)

Thirty‐four novel α/β‐tetrapeptides ( 1–34 ) have been prepared employing solid‐phase and in‐parallel synthetic protocols. α/β ‐Tetrapeptides 1 – 34 were prepared by a combination of three α‐amino acid residues (alanine (Ala), phenylalanine (Phe), and isoleucine (Ile)) with one β‐amino acid residue (β³‐homophenylglycine). The corresponding complexes of several selected α/β‐tetrapeptides with alkali, alkaline earth, and transition metals, [tP + M⁺], were evaluated using ion electrospray‐ionization mass spectrometry (ESI‐MS). According to the results from analysis of mixtures, we can conclude that the position of the β‐amino acid is determinant in the affinity toward different metal cations. Computational modeling (DFT, B3LYP 6‐311++G) provided useful information regarding the most likely coordination sites of the metal ions on the receptor α/β‐tetrapeptide 12 , HO₂C‐α‐Phe‐α‐Phe‐α‐Ile‐β³‐hPhg‐NH₂, as well as the conformational changes induced by the metal upon [tP + M⁺] complex formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Inclusion of menadione with cyclodextrins studied by calorimetry and spectroscopic methods

Complex formation of menadione with α‐, hydroxypropyl α‐, β‐, hydroxypropyl‐β‐, methyl‐β‐ and hydroxypropyl‐γ cyclodextrins in aqueous solution at 298.15 K was studied by using isothermal titration calorimetry, ¹H NMR, and UV–vis spectrophotometry. The experimental data indicated the partial insertion of menadione into macrocyclic cavity upon formation of two alternative types of 1:1 inclusion complexes, whose thermodynamic parameters (K, Δ_cG⁰, Δ_cH⁰, and Δ_cS⁰) were calculated. The influence of host size on the complex formation process was analyzed. β‐Cyclodextrin and its hydroxypropylated and methylated derivatives were found more effective binders towards menadione than α‐ and γ‐cyclodextrins. Copyright © 2007 John Wiley & Sons, Ltd.     

Comparative Raman spectroscopic analysis of orientation in fibers and regenerated films of Bombyx mori silk fibroin

This study is focused on the Raman spectroscopic analysis of degummed silk fibroin (SF) fibers and regenerated Bombyx mori silk fibroin films: a correlation was found between some spectral features related to the methylene deformation modes and the molecular orientation of the samples. Polarized Raman spectra on SF fibers were used to obtain the orientation distribution function of carbonyl groups along the protein backbone. The variation of the intensity ratio of 1400/1450 cm⁻¹ for the peaks attributed to the wagging and bending deformation modes of CH₂ groups with respect to the angular orientation of the fiber was measured and quantitatively correlated with the orientation distribution function of the carbonyl groups. Unpolarized Raman spectra were measured for regenerated silk fibroin films and lyophilized solutions. The variation of the intensity ratio of 1415/1455 cm⁻¹, which is related to the deformation modes of CH₂ groups in SF regenerated materials, was qualitatively related to the microstructural orientation of the samples observed by scanning electron microscopy (SEM), and to the presence of Silk I phase as suggested by the analysis of samples obtained in different casting conditions and also by the measurements on mechanically deformed films. The results obtained showed the utility of the spectroscopic intensity ratio of 1400/1450 cm⁻¹ for the rapid assessment of molecular orientation in silk fibers, which could be useful for quality and process control of regenerated silk‐based textiles. Moreover, the qualitative dependence of the intensity ratio of 1415/1455 cm⁻¹ was found to be sensitive to both the microstructural orientation and Silk I content of regenerated silk fibroin films, suggesting a possible correlation of this Raman marker of the Silk I phase with the degree of molecular order brought about by this polymorph. Copyright © 2006 John Wiley & Sons, Ltd.     

Environmentally friendly surface modification of silk fiber: Chitosan grafting and dyeing

In this paper, the surface modification of silk fiber using anhydrides to graft the polysaccharide chitosan and dyeing ability of the grafted silk were studied. Silk fiber was degummed and acylated with two anhydrides, succinic anhydride (SA) and phthalic anhydride (PA), in different solvents (dimethyl sulfoxide (DMSO) and N,N-dimethyl formamide (DMF)). The effects of anhydrides, solvents, anhydride concentration, liquor ratio (L:R) and reaction time on acylation of silk were studied. The polysaccharide chitosan was grafted to the acylated silk fiber and dyed by acid dye (Acid Black NB.B). The effects of pH, chitosan concentration, and reaction time on chitosan grafting of acylated silk were investigated. The physical properties show sensible changes regardless of weight gain. Scanning electron microscopy (SEM) analysis showed the presence of foreign materials firmly attached to the surface of silk. FTIR spectroscopy provided evidence that chitosan was grafted onto the acylated silk through the formation of new covalent bonds. The dyeing of the chitosan grafted-acylated silk fiber indicated the higher dye ability in comparison to the acylated and degummed silk samples. The mechanism of chitosan grafting over degummed silk through anhydride linkage was proposed. The findings of this research support the potential production of new environmentally friendly textile fibers. It is worthwhile to mention that the grafted samples have antibacterial potential due to the antibacterial property of chitosan molecules.     

Inclusion complexes of estrone and estradiol with β‐cyclodextrin: Voltammetric and HPLC studies

The interaction of estrone and estradiol with β‐cyclodextrins (βCD) was investigated by differential pulse voltammetry (DPV) and high‐performance liquid chromatography (HPLC) in mixed media. The co‐solvent influence on the tendency of these estrogens to form inclusion complexes with βCD was examined. Thus, acetonitrile (MeCN) and ethanol (EtOH) were used in a mixed aqueous medium containing phosphate buffer. The association constant of the inclusion complexes (K_a) of estrone and estradiol with βCD were determined in two different media by using both voltammetric and chromatographic techniques. Estradiol was found to bind to βCD with higher affinities than estrone, irrespective of the medium. We have also found a clear influence of the co‐solvent on the K_a value, which means a competition of co‐solvent molecules with estrogens for binding to the cavity of βCD. Consequently, interaction between βCD and the steroids is weakened when acetonitrile is used. Copyright © 2007 John Wiley & Sons, Ltd.     

Silver nanoparticle containing silk fibroin bionanotextiles

Development of new generation bionanotextiles is an important growing field, and they have found applications as wound dressings, bandages, tissue scaffolds, etc. In this study, silver nanoparticle (AgNP) containing silk-based bionanotextiles were fabricated by electrospinning, and processing parameters were optimized and discussed in detail. AgNPs were in situ synthesized within fibroin nanofibers by UV reduction of silver ions to metallic silver. The influence of post-treatments via methanol treatment and glutaraldehyde (GA) vapor exhibited changes in the secondary structure of silk. Methanol treatment increased the tensile properties of fibers due to supported crystalline silk structure, while GA vapor promoted amorphous secondary structure. AgNP containing silk fibroin bionanotextiles had strong antibacterial activity against gram-positive Staphylococcus aureus and gram-negative Pseudomonas aeruginosa.     

Structural changes of thin films from recombinant spider silk proteins upon post-treatment

Engineering of spider silk proteins offers the possibility to control their molecular sequence and thus their material properties. Spin coating was used to prepare films of engineered spider silk protein derived from the garden spider’s (Araneus diadematus) dragline silk protein ADF-4. A conformational transition from α-helix to β-sheet-rich structures upon methanol treatment of the films was detected by external reflection IR spectroscopy. We present direct evidence for this structural transformation using grazing-incidence X-ray diffraction (GIXRD) and small-angle scattering (GISAXS). The protein film structure after the methanol treatment consists mainly of β-sheet polyalanine crystals dispersed in an amorphous protein matrix. The GIXRD intensity profiles show Bragg peaks from β-sheet polyalanine crystallites having an average size of 7.5 nm. The non-uniform and large crystal size distributions within the film were explained based on the protein composition. The effect of the chemical nature of the interface on the protein film structure was investigated as well. PACS 87.15.-v; 68.55.-a; 61.10.Eq     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Anti-fouling poly(2-hydoxyethyl methacrylate) surface coatings with specific bacteria recognition capabilities

Poly(2-hydroxyethyl methacrylate), PHEMA, brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) on silanized glass slides bearing grafted initiators. High resolution X-ray photoelectron spectroscopy (XPS) highlighted the surface chemical changes of the glass slides upon silanization and surface-confined ATRP of HEMA. Particularly, the initiator sites from the silane were detected by their bromine Br3d core electron peak whilst the O/C atomic ratios and the high resolution C1s region of the glass–PHEMA hybrids are comparable to those of pure PHEMA, thus confirming that the PHEMA chains have indeed attached to the surface. The glass–PHEMA hybrids were found to behave as anti-fouling ultrathin coatings as they resisted non-specific Salmonella typhimurium bacterial adhesion. This behaviour is driven by the hydrophilic properties of the glass–PHEMA hybrids which were assessed by contact angle measurements. In contrast, after activation of PHEMA brushes by S. typhimurium antibodies through the trichlorotriazine coupling procedure, the bacteria specifically and strongly attached to the PHEMA-coated glass slides as judged from optical microscope observation.     

Tribological Properties of Polycarbonate Blended with High‐density Polyethylene and High‐density Polyethylene Grafted with Maleic Anhydride

High‐density polyethylene (HDPE) and maleic anhydride grafted HDPE (HDPE‐g‐MA) were selected as lubricant and compatibilizer, respectively, for improving the tribological and mechanical properties of polycarbonate (PC). The morphology of worn surfaces and debris was observed by means of scanning electron microscopy (SEM). The mated steel ring surface was analyzed by using SEM combined with energy dispersive spectroscopy (EDS). Both HDPE and HDPE‐g‐MA reduced the friction and wear of pure PC. HDPE‐g‐MA, which had a better compatibility with PC than HDPE, resulted in better improvement of the mechanical and tribological properties of the PC matrix. A 10 vol. % HDPE‐g‐MA reduced the wear of pure PC by 4 orders of magnitude, and the friction coefficient was reduced from 0.86 to 0.22. Such improvements in the tribological behavior resulted from the good self lubrication of HDPE and HDPE‐g‐MA. The PC/HDPE‐g‐MA (S_90‐0‐10) polyblend also showed higher notched impact strength than pure PC. It may be a useful material for application in tribological fields.     

Reaction of poly‐L‐lysine with aryl acetates and aryl methyl carbonates. A mechanistic study

The pH profile (log k vs. pH) of the reactions of poly‐L ‐lysine (PL) with a series of aryl acetates and aryl methyl carbonates in aqueous solution show the same conformational changes as those determined by potentiometric titrations. When PL is a random coil, the most probable mechanism for the reactions studied is through the formation of a tetrahedral intermediate and its breakdown to products as the rate‐determining step. The tetrahedral intermediate is stabilized by a hydrogen bond interaction between the nitro groups in the substrate and the NH group of the principal chain or some NH₂ groups of the lateral chains. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of novel bis(β‐cyclodextrin)s linked with aromatic diamine and their molecular recognition with model substrates

Novel β‐cyclodextrin (β‐CD) dimers with aromatic diamine linkers, 1,3‐(aminomethyl)‐benzylamine‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (2) , 4,4′‐diaminodiphenylmethano‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (3) , and 4,4′‐ ethylenedianiline‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (4) , were synthesized. The inclusion complexation behaviors of these compounds, together with 4,4′‐aminophenyl ethyl‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (5) , with substrates such as acridine red (AR), neutral red (NR), ammonium 8‐anilino‐1‐naphthalenesulfonate (ANS), sodium 2‐(p‐toluidinyl) naphthalenesulfonate (TNS), rhodamine B (RhB), and brilliant green (BG), were investigated by ultraviolet, fluorescence, circular dichroism, and 2D NMR spectroscopy. The results indicated that the two linked CD units cooperatively bound to a guest, and the molecular binding affinity toward substrates, especially curved guest ANS and linear guests such as NR and AR, was increased. The linker length between two CD units played a crucial role in the molecular recognition of the hosts with guest dyes. The binding constants of the hosts for AR, TNS, ANS, and RhB decreased with increasing linker length in hosts 2‐4 . Moreover, structurally similar hosts 3 and 5 exhibited very different binding behavior for the guests. Host 5 showed much higher Ks values toward positively charged guests and lower Ks toward negatively charged guests than host 3 . The 2D NMR spectra of hosts 3 and 5 with RhB were acquired to understand the binding difference between 3 and 5 . The molecular binding ability and selectivity of model substrates by these hosts were sufficiently investigated to reveal not only the cooperative contributions of the linker group and CD cavities upon inclusion complexation with dye guest molecules, but also the controlling factors for the molecular selective binding. Copyright © 2008 John Wiley & Sons, Ltd.