Conformational transitions of poly(β-benzyl L-aspartate)

Conditions that affect the conformation of poly(β-benzyl L-aspartate) in films have been studied. A slow transition from the left-handed to the right-handed α-helical form is observed under certain conditions in half-dried film cast from chloroform solutions and after exposure of amorphous films of the left-handed β-helical form to chloroform vapor. This transition is caused by adsorption of moisture. Thermal transitions of these films were examined by differential scanning calorimetry and infrared spectroscopy. The right-handed α-helices change to left-handed ω-helices around 140°C, and sharp exothermic peak is observed in this region for some films.     

Photoinduced conformational changes of azoaromatic polyaspartates containing octadecyl side chains

Copolymers of p-(phenylazo)benzyl-L-aspartate and n-octadecyl-L-aspartate exist as right- and left-handed α-helices in solution at 25°C depending on the copolymer composition: the reversal of helix sense from a right- to left-handed one occurs with increasing the azobenzene content. The α-helices of the copolymers are very sensitive to trifluoroacetic acid (TFA), and are converted into random coil below 2.0% of TFA. Among the copolymers, the copolymer containing 47% azobenzene groups is unique since it exhibits a TFA-induced conformational change from right-handed α-helix to random coil via left-handed α-helix. Upon UV light irradiation at 25°C, the copolymers containing 68 and 89% azobenzene groups caused the reversal in helix sense from a left- to right-handed one. The conformations of the copolymers were dependent on temperature, mostly right-handed and left-handed α-helices at lower and higher temperatures, respectively. On this basis, the copolymer containing 47% azobenzene groups could be made to undergo a photoinduced helix reversal at high temperatures.     

Carbon-13 NMR chemical shift and electronic structure of polypeptide as studied by tight-binding MO theory: poly (β-benzyl L-aspartate) with the right-handle α-helix and left-handed α-helix forms

An attempt was made to calculate ¹³C NMR chemical shifts of poly(β-benzyl L-aspartate) having the right-handed α-helix (α_R-helix) and left-handed α-helix (α_L-helix) forms by a tight-binding MO sum-over-states theory within the extended Hückel framework, in order to examine whether or not the conformation-dependent ¹³C chemical shifts previously determined by the cross polarization-magic angle spinning technique are reproduced by a change of electronic structure of the polymer. It is found that the relative displacements of the observed C_α, C_β and carbonyl ¹³C chemical shifts between the α_R- and α_L-helices are reproduced qualitatively by the calculation.     

Piezoelectric properties of oriented films of poly(γ-methyl D-glutamate)

The dynamic piezoelectric stress constant e^*₂₅ of drawn films of poly(γ-methyl D -glutamate) (PMDG) cast from solutions in α-helix-promoting solvents 1,2-dichloroethane (DCE) and chloroform and from the nonhelicogenic solvent dichloroacetic acid (DCA) was measured from ?180°C to 200°C at 110 Hz. The drawn and annealed films cast from chloroform show a small peak for the real part of piezoelectric stress constant ?e′₂₅ in the temperature range of the mechanical α₂-crystalline relaxation, which is caused by the distortion motion of the backbone chain of the α-helix. On the other hand, drawn films cast from DCE show the peak of the real part of the piezoelectric stress constant, whose magnitude decreases in the range of the mechanical α₁-crystalline relaxation or the β-relaxation processes, which were previously ascribed, respectively, to mutual slipping of α-helices and to the micro-Brownian motion of disordered regions. Also, ?e′₂₅ becomes virtually zero near 180°C where the α₂-relaxation is located. These results suggest that the polarization change induced by applied strain is caused by distortion of the backbone chains in the α-helix. Near 0°C, the temperature range of the side-chain mechanical relaxation, ?e′₂₅ exhibits a marked peak both for films cast from chloroform and from DCE. The maximum value of ?e′₂₅ and the orientation function of the α-helix axis are linearly related and extrapolation of ?e′_25,max to unit orientation function gives 1.3 × 10⁴ cgs esu which corresponds to 2.4 Debye per residue. This value corresponds reasonably to the value of 3.71 Debye for the permanent dipole moment of NHCO bond if the correction for crystallinity is made. This result also indicates the piezoelectric properties of PMDG arise from distortion of the backbone chain of the α-helix induced by applied strain.     

Structure and molecular conformation of tussah silk fibroin films: Effect of methanol

Structural changes of tussah (Antheraea pernyi) silk fibroin films treated with different water-methanol solutions at 20°C were studied as a function of methanol concentration and immersion time. X-ray diffraction measurements showed that the α-helix structure, typical of untreated tussah films, did not change for short immersion times (2 min), regardless of methanol concentration. However, crystallization to β-sheet structure was observed following immersion of tussah films for 30 min in methanol solutions ranging from 20 to 60% (v/v). IR spectra of tussah films untreated and methanol treated for 2 min exhibited strong absorption bands at 1265, 892, and 622 cm^?1, typical of the α-helix conformation. The intensity of the bands assigned to the β-sheet conformation (1245, 965, and 698 cm^?1) increased for the sample treated with 40% methanol for 30 min. Raman spectra of tussah films with α-helix molecular conformation exhibited strong bands at 1657 (amide I), 1263 (amide III), 1106, 908, 530, and 376 cm^?1. Following α → β conformational transition, amide I and III bands shifted to 1668, and to 1241, 1230 cm^?1, respectively. The band at 1106 cm^?1 disappeared and new bands appeared at 1095 and 1073 cm^?1, whereas the intensity of the bands at 530 and 376 cm^?1 decreased significantly. ©1995 John Wiley & Sons, Inc.     

Persistent polarization in poly(vinylidene fluoride). III. Depolarization and pyroelectricity of poly(vinylidene fluoride) thermoelectrets

Persistent polarization in poly(vinylidene fluoride) thermoelectrets prepared under high electric field has been studied by measurements of depolarization and pyroelectricity. Various polarizations are examined in detail; the polarizations related to a characteristic molecular motion near 60°C and the polarizing temperature are not responsible for the major piezoelectric effect in β-form electrets. The piezoelectricity is attributed to a polarization appearing near the melting temperature. The persistent polarization corresponding to d₃₁ of 2 × 10^?11 coul/N is about 5 × 10^?6 coul/cm². The pyroelectricity of β-form electrets is linearly correlated with the piezoelectricity.     

Structural changes induced in tussah silk (Antheraea pernyi) fibroin films by immersion in methanol

The crystalline transition induced by immersion in a methanol/water mixture of tussah silk fibroin (from Antheraea pernyi) film obtained by casting from a 1% solution was studied by x-ray diffraction, differential scanning calorimetry, and infrared spectroscopy. The molecular conformation of the fibroin, consisting mostly of the α-helix and random-coil forms, was transformed into a random-coil and β-rich conformation containing only a small amount of α-helix after immersion for no more than 5 min. The intersheet packing of the β-crystal of the original tussah silk fibroin film was imperfect in the early stage of immersion. However, crystallization proceeded further when the immersion time exceeded 10 min. As a result the sheets in the β-form crystal became closely packed because of the decrease in the content of the random-coil form. The exothermic peak, which appeared at 226°C in the original fibroin and was attributed to the random-coil → β-structure transition, disappeared completely after immersion for 5 min.     

Studies on the β-crystalline form of isotactic polypropylene

A study has been made of the mechanical, thermal, and morpholigical characteristics of melt-crystallized isotactic polypropylene containing high levels of the β or pseudohexagonal crystalline form. Different levels of β-form crystallinity were produced in the polymer by blending in low levels of quinacridone dye nucleating agent. Microscopical studies of the crystallization process revealed that both α-form (monoclinic), and β-form spherulites nucleated on the dye particles, with α-spherulite growth commencing at a higher temperature. These observations were able to qualitatively explain the dependence of β-form level on both the nucleant concentration and its state of dispersion in the polymer. Improving the dispersion of the nucleant was found to reduce the level of β-form crystallinity if the nucleant concentration exceeded an optimum level. A new procedure for quantifying the volume fraction of β spherulites in a sample was developed which utilized the technique of selective solvent extraction. From volume-fraction, x-ray, and density data, the pure α and β crystal densities were obtained. Dynamic mechanical measurements-obtained on unoriented specimens containing varying levels of β-form crystallinity showed an increase in the magnitude of the damping in the post-T_g region with increasing β content. High levels of the β form lead to lower values of the modulus and yield stress, and higher values of the elongation at break and impact strength.     

Crystal Transformation and Development of Tensile Properties upon Drawing of Poly(L-lactic acid) by Solid-State Coextrusion: Effects of Molecular Weight

Melt-crystallized films of poly(L -lactic acid) (PLLA) with M_v in the range of 3.8 ∼ 46 × 10⁴ consisting of α-form crystals were uniaxially drawn by solid-state coextrusion. The effects of M_v, extrusion draw ratio (EDR), and extrusion temperature (T_ext) on the crystal/crystal transformation from α- to β-form crystals and the resultant tensile properties of drawn products were studied. The crystal transformation proceeded with EDR and more rapidly for the higher M_v's. Furthermore, the crystal transformation proceeded most rapidly with EDR at a T_ext around 130 °C, independently of the M_v's. As a result of the optimum combination of processing variables influencing the the crystal transformation (M_v, T_ext, and drawability), highly oriented films consisting of β-form crystals alone were obtained by coextrusion of higher M_v samples at T_ext's slightly below the melting temperature (150 ∼ 170 °C) and at higher EDR's > 11. Both the tensile modulus and strength increased rapidly with EDR. The modulus at a given EDR was slightly higher for the samples with higher M_v's. In contrast, the strength at a given EDR was remarkably higher for the higher M _v's. The highest tensile modulus of 8.0 GPa and strength of 500 MPa were obtained with the sample of the highest M_v of 46 × 10⁴ coextruded at 170 °C to the highest EDR of 14.     

最短α-螺旋的理论研究

在B3LYP/6-31+G**水平下的溶剂中优化得到4个残基长和5个残基长的α-螺旋. 计算得到的骨架构象与蛋白质晶体结构的统计结果符合得很好. 类似于一般的较长α-螺旋, 观察到了C-端的散开. 对很短的聚丙氨酸肽链, 从焓上看310-螺旋明显比α-螺旋稳定, 然而熵效应不利于310-螺旋结构. 螺旋N2(N-端第二个残基)位上天冬氨酸侧链的加盖(Capping)效应明显使α-螺旋相对310-螺旋更加稳定. 因而, 在同样长度下α-螺旋比310-螺旋多的统计结果能够被理解. 另外, 最短的α-螺旋的C-端倾向于以β-转角结构结束.     

Solid-state polymerization of long-chain vinyl compounds. I. Effect of molecular arrangement on polymerizability of octadecyl methacrylate

γ-Ray-initiated postpolymerization of octadecyl methacrylate in polymorphic crystals and melt has been investigated to clarify the effect of molecular arrangement of the monomer on polymerizability. From thermal, x-ray, and infrared (IR) analyses this long-chain monomer exhibited three crystalline modifications that we refer to as α-, sub-α, and β-forms. The β-form (mp 28.7–29.7°C), which is obtainable from solution, is a stable state with triclinic chain packing. The α-form (mp 19.5–20.0°C), which is obtained first from the melt but transforms into β-form on storing, is a metastable state with hexagonal chain packing. The sub-α-form appears transiently in α→β transition. The polymerizability of octadecyl methacrylate in the β-form is extremely low, whereas the α-form can polymerize easily and the initial polymerization rate, saturated conversion, and polymer molecular weights increase with temperature. Polymerizability in the molten state at fairly high temperature is rather low, however. Thus maximum polymerizability is obtained just above the melting point of α-form. It has been found that particular orientation and suitable packing mode with some freedom of rotational motion of the monomer molecules in layered structure accelerate the polymerization reaction.     

Structural Investigation of Hybrid Peptide Foldamers Composed of α-Dipeptide Equivalent β-Oxy-δ5-amino Acids

Due to their equivalent lengths, δ-amino acids can serve as surrogates of α-dipeptides. However, δ-amino acids with proteinogenic side chains have not been well studied because of synthetic difficulties and because of their insolubility in organic solvents. Recently we reported the spontaneous supramolecular gelation of δ-peptides composed of β(O)-δ⁵-amino acids. Here, we report the incorporation of β(O)-δ⁵-amino acids as guests into the host α-helix, α,γ-hybrid peptide 12-helix and their single-crystal conformations. In addition, we studied the solution conformations of hybrid peptides composed of 1:1 alternating α and β(O)-δ⁵-amino acids. In contrast to the control α-helix structures, the crystal structure of peptides with β(O)-δ⁵-amino acids exhibit α-helical conformations consisting of both 13- and 10-membered H-bonds. The α,δ-hybrid peptide adopted mixed 13/11-helix conformation in solution with alternating H-bond directionality. Crystal-structure analysis revealed that the α,γ⁴-hybrid peptide accommodated the guest β(O)-δ⁵-amino acid without significant deviation to the overall helix folding. The results reported here emphasize that β(O)-δ⁵-amino acids with proteinogenic side chains can be accommodated into regular α-helix or 12-helix as guests without much deviation of the overall helix folding of the peptides.     

A study of the conformational stability of poly(β-benzyl l-aspartate), poly(γ-benzyl l-glutamate) and poly(β-benzyl l-aspartate)/poly(γ-benzyl l-glutamate) blend in the solid state by variable-temperature C CP/MAS NMR

¹³C CP/MAS NMR experiments on polypeptides, poly(β-benzyl l-aspartate) (PBLA), poly(γ-benzyl l-glutamate) (PBLG) and PBLA/PBLG blend have been carried out, in order to elucidate the conformational stability of the polypeptides in the solid state over a wide range of temperatures and its blending effect. The PBLA/PBLG blend with a mixture ratio of 1/1 is prepared by adding trifluoroacetic acid (TFA) solution to alkaline water (TFA-alkaline treatment). From these experimental results, it is found that the conformation of PBLA in the PBLA/PBLG blend sample is changed from left-handed helix (α_L-helix and/or ω_L-helix) form to the α_R-helix form, and then the origin of the formation of the α_R-helix form in PBLA comes from the existence of PBLG. Further, from the variable-temperature ¹³C CP/MAS NMR experiments results, it is shown that the conformational behavior of PBLA in the PBLA/PBLG blend is similar to that of the TFA-alkaline treated PBLA, and also the conformational behavior of PBLG in the PBLA/PBLG blend is similar to that of the TFA-alkaline treated PBLG.     

Fabrication of starch blend films with different matrices and their mechanical properties

The objective of the study was to determine the effects of molecular sizes of amylose (AM) and starch granules on the mechanical properties of thermoplastic starch (TPS) blend films. Leached amylose solution from cassava (CS_ AM) and mung bean (MB_AM), and two forms of amylopectin (AP) (granular; g and non-granular; ng) of waxy cassava (WxCS) starch were used. Four types of film matrices were fabricated and all TPS blend films contained same amount of AM and glycerol. Results displayed that molecular weight profiles of starch films and presence of granule remnants significantly controlled the film matrix formation, types of crystal formation, and percent of relative crystallinity (%RC) (p < 0.05). Tensile property of TPS films was controlled by %RC and presence of granule remnants. Percent elongation at break (%E_b) of TPS films increased when the films had a large range of molecular weight distribution (from 5.5 × 10⁷ g/mol to 0.4 × 10⁵ g/mol) and contained a high weight fraction (~58%) of starch molecules with M_w~0.4 × 10⁵ g/mol.     

Optical activity of small peptide chains with right-handed α-helix structure

The optical activity of oligopeptides in the conformation of the right-handed α-helix was calculated by the direct semiempirical quantum chemical CNDO /OPTIC method. The oligomers of glycine and alanine from dimer up to pentamer were considered. The comparison with results obtained using the model of interacting groups (MIG ) based on the perturbation approach was carried out. The calculational results show that the circular dichroism (CD ) of oligopeptide α-helices is essentially different from the CD of the peptide polymers in the same conformation. The comparison between results obtained by the CNDO /OPTIC method and by the MIG leads to doubts about the reliability of the use of the MIG to calculate rotatory strengths of nπ* transitions of oligopeptides in α-helix conformation.     

成核剂含量对β晶相聚丙烯结晶与熔融行为的影响

用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005％时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.     

β型聚丙烯注塑件的分层结构与力学性能

用X-射线衍射仪研究了不加和加成核剂形成不同晶型的三种聚丙烯注塑件的分层结晶结构,获得各层结晶度和β晶型含量(k_β)随皮芯距离的分布规律,测定了试件弯曲、拉伸和冲击性能。发现,纯等规聚丙烯试件主要含α晶型,皮层的结晶度和k_β低于芯层。加有α成核剂的试件仅含有α晶型,皮层的结晶度也低于芯层。加有β成核剂的试件主要含β晶型,皮层的结晶度和k_β值高于芯层。纯聚丙烯试件和β型为主的试件的分层结构中存在α晶和β晶间的转变。与α型聚丙烯相比,β型聚丙烯有较低的屈服强度,却有较高的抗张强度,显示很高的拉伸韧性和延展性,可明显提高室温以及玻璃化温度以下的低温抗冲击性能。     

Expanding the conformational pool of cis-beta-sugar amino acid: accommodation of beta-hGly motif in robust 14-helix

Tendencies of forming stable helices of heterooligomers composed of alternating rigid cis-beta-sugar amino acid and flexible beta-hGly motifs have been investigated, using a combination of molecular mechanics, CD, FT-IR, and NMR techniques. The results show that the solution structures of these oligomers exist as robust right-handed 14-helices. Here, we examine the role of conformationally rigid cis-beta-sugar amino acid in preorganizing the conformation of beta-hGly to form the 14-helix. Our findings also show that a right-handed 14-helix can be formed with as few as four properly sequenced heterogeneous residues. These results represent the expansion of the conformational pool of sugar amino acid in the design of well-folded 14-helices, which can be used to develop beta-peptides endowed with biological activity.     

拉伸对聚左旋乳酸结晶的影响

在成型加工过程中,拉伸是提高聚合物材料结晶能力的一种重要手段. 本文采用红外光谱、差示扫描量热分析、X射线衍射等方法系统研究了不同温度下拉伸对聚左旋乳酸（PLLA）结晶行为的影响. 结果表明,在合适的温度条件下,拉伸能迅速提高PLLA的结晶速度和结晶度. 对经过拉伸预处理但未结晶的PLLA样品进行等温及非等温结晶的研究发现,经过拉伸预处理的PLLA样品的结晶速率和结晶度都得到提高,这表明预拉伸会影响PLLA在后续过程中的结晶行为.     

A STUDY OF LOW-TEMPERATURE CRYSTALLIZATION BEHAVIOR THE cis-1,4 POLYBUTADIENE PREPARED WITH RARE-EARTH CATALYST SYSTEM

The effects of molecular weight and temperature on crystallization processes at low tempera-ture for cis-1,4 polybutadiene prepared with rare-earth catalyst (Ln-PB) have been studied by WAXDmethod. In the range of molecular weight from