Electronic and molecular structures of HCNn polymers: (HCN)3n

The CNDO/2 method using the tight-binding approximation for polymers was applied to several forms of (HCN)_3n polymers. From these calculations, we conclude that the polymer exists in the helical form rather than the planar trans zigzag, TTT, form. It was found that, from comparison of the TTT form with the polyglycine II type (Gly-II) form, the intrasegment energy of the TTT form is lower than for the Gly-II type form while the intersegment energy of the Gly-II form is lower than for the TTT form. It was also revealed that, in the typical α-helix type structures, hydrogen bonding between the central and the fourth nearest neighbour segments may play an important stabilizing role.     

间规聚苯乙烯同质多晶现象的研究

间规聚苯乙烯(ｓＰＳ)是由日本出光公司在1985年首先合成,由于其优良的耐热性(熔点高达270℃),立刻被认为有可能或为下一世纪最重要的工程塑料.独特的分子结构,使间规聚苯乙烯具有密度低、尺寸稳定、耐热性、耐溶剂性好等诸多优点,因而引起研究人员的广泛重视.同时,间规聚苯乙烯存在复杂的同质多晶现象,共有α、β、γ和δ四种晶型.以不同的条件从熔体结晶,间规聚苯乙烯可形成平面锯齿结构的α晶和β晶.其中,α晶属六方晶系,晶胞参数为:ａ=263ｎｍ,ｃ=078ｎｍ;β晶是斜方晶,晶胞参数为:ａ=088ｎｍ,ｂ=263ｎｍ,ｃ=078ｎｍ.与传统的全同聚丙烯…     

Direct probing of zwitterion formation in unsolvated peptides

Molecular beam electric deflection measurements have been used to determine electric susceptibilities for small unsolvated alanine-based peptides. The electric susceptibility provides information about the charge distribution within the peptide and can be used to distinguish between zwitterionic and canonical forms. Measured electric susceptibilities for WAn peptides (n = 1-5) are similar to those for capped Ac-WAn-NH2 peptides (which cannot form zwitterions). Susceptibilities calculated using a simulated tempering-based approach are substantially larger for the zwitterionic form than for the canonical form. The measured susceptibilities are in good agreement with those calculated for the canonical form. For the larger peptides, the lowest potential energy structure found in the simulations is hairpin-like, while the lowest free energy structure found at room temperature is extended. The zwitterionic form is constrained by intramolecular interactions which make it entropically unfavorable.     

Ab initio Study of the Keto-Enol Equilibriumof Malonaldehyde

 The mechanism of the keto-enol tautomerism of malonaldehyde was studied by ab initio methods using 6-21G^** and 6-311G^** basis functions at the HF level. Two separate mechanisms were examined: through-space proton transfer in the ω-shaped form and through-space proton transfer in a sickle-shaped form obtained from the ω form by rotation. The transition state structure of the ω form is non-planar, whereas that of the sickle form is planar. The sickle form is connected with a 2^nd order saddle, indicating that there should exist a lower energy barrier, i.e. that the through-bond mechanism may be preferred. The calculated energy barriers of keto-enol tautomerism for the sickle form is twice as high as those for the omega form.     

Biological selection of peptides for poly(l-lactide) substrates

Short peptides that recognize the alpha form of poly( l-lactide) (PLLA) crystalline films were identified from a phage-displayed peptide library. An enzyme-linked immunosorbent assay (ELISA) revealed that the apparent binding constants of the phage clones for the alpha form of PLLA were greater than those of the unselected phage library. The specificity index for the alpha form of PLLA referred to a structurally similar atactic poly(methyl methacrylate) (at-PMMA), supporting the alpha form of PLLA specific binding of the selected phage. Amino acid residues with proton-donor lateral groups and hydrophobic alkyl groups were relatively enriched in a sequence of heptapeptides on the specific phage clones, thereby suggesting the presence of hydrogen bonding as well as hydrophobic interactions between the alpha form of PLLA and the peptides. Surface plasmon resonance (SPR) analysis revealed that the binding constant of the freed c22 heptapeptide (Gln-Leu-Met-His-Asp-Tyr-Arg) for the alpha form of PLLA was greater than those for reference at-PMMA, amorphous PLLA, and the beta form of PLLA. It was found that c22 peptide can recognize slight differences in PLLA polymorphs such as a crystalline state and an arrangement of PLLA functional groups.     

用ab initio方法研究NaN_3的几何构型、电子结构和热力学、动力学性质

用ａｂｉｎｉｔｉｏＭＯ方法，在ＭＰ２（ｆｕｌ）／６３１１Ｇ水平下，全优化计算了叠氮化钠（ＮａＮ３）分子的线状和环状两种稳定构型及其转化过渡态的几何参数、电荷分布、分子总能量和振动频率，并研究了它们的热力学性质及转化速率常数和平衡常数．结果表明，线状比环状构型稍稳定（能量低６．０４ｋＪ／ｍｏｌ）；两者相互转化的能垒分别为１３．１５ｋＪ／ｍｏｌ（线型→环状）和７．１１ｋＪ／ｍｏｌ（环状→线型）．热力学和动力学计算均表明：ＮａＮ３通常主要以线型结构存在（占８５％以上），且随温度升高而增多（在１０００Ｋ大于９１％）．     

Thermally-Induced Phase Transitions in the Uniaxially-Oriented δ Form of Syndiotactic Polystyrene

The empty δ (δ_e) form of uniaxially-oriented syndiotactic polystyrene (sPS) samples were obtained by extracting the solvent molecules from the δ form of sPS and solvent complex in acetone and methanol. Temperature dependence of the X-ray fiber diagrams starting from the uniaxially-oriented δ_e and δ form has been measured successfully at various temperatures for the first time. The transition behavior was traced clearly by separating the equatorial and layer line reflections. The δ_e form transformed to the γ form via an intermediate form. The intermediate form is speculated to take disordered structure due to the empty cavities present in the δ_e form. Calorimetric studies showed an endotherm followed by an exotherm during this phase transition, which is consistant with such a speculation. On the other hand the δ form transformed to the γ form directly without passing through the intermediate form or δ_e form. During the δ to γ phase transition the solvent molecules evaporate through the columnar structure in a broad range of temperature, allowing the transition to occur smoothly.     

Antifreeze Protein‐Induced Selective Crystallization of a New Thermodynamically and Kinetically Less Preferred Molecular Crystal

The formation of a new, dihydrate crystalline form of 5‐methyluridine (m⁵U) was selectively induced by a protein additive, antifreeze protein (AFP) in a highly efficient manner (in 10^?6 molar scale, whereas known kinetic additives need 0.1 molar scale). The hemihydrate form (form I, the only previously known crystalline form of m⁵U) and the dihydrate form of m⁵U (form II) obtained herein were characterized using X‐ray crystallography and differential scanning calorimetry (DSC). Compared to form I, remarkably, form II is thermodynamically and kinetically less preferred. The presence of AFP can selectively inhibit the appearance of form I and hence allows the growth of form II, the pure form of which cannot grow directly from m⁵U supersaturated solutions under the same conditions. An explanation supported by both experimental and theoretical results is provided for the AFP‐induced selection process. Implications on AFP‐induced ice shape changes are also discussed. Control of crystallization from supersaturated solutions is of great interest in both fundamental research and practical applications in fields like chemistry, pharmacology and materials science. These findings suggest that crystallization processes with AFPs could be valuable for selective growth of hydrates and polymorphs of important pharmaceutical compounds.     

The behavior of the form factor in two dimensions for linear polymers in different regimes

Off-lattice Monte Carlo simulations employing the PIVOT algorithm are used to generate ideal and excluded volume linear polymers in two dimensions. The form factor at small and large wave vectors is calculated from the resulting configurations and compared to the exact equation for ideal chains and to both scaling and renormalization group predictions for excluded volume chains. It is found that using the des Cloizeaux form for the distance distribution function in an analytic calculation of the form factor leads to close agreement with the Monte Carlo data and that simple expressions for both the small and large wave vector expansions reproduce the essential features of the form factor.     

Mechanical relaxation in polypropylene as a function of polymorphism and degree of lamella orientation

Mechanical relaxation data as a function of temperature (ca. 1 Hz) have been obtained for several samples of isotactic polypropylene crystallized from the melt, which exhibit both α and β forms as well as varying degrees of lamella orientation. The samples ranged in morphology from an unoriented sample showing only the α form to one highly oriented having approximately 90 per cent the β form. Results for the logarithmic decrement Δ and loss modulus G″ are that the low temperature (ca. ?75°C) and glass temperature (ca. 0°C) relaxations show little or no sensitivity to orientation in the α form, but that the intensity of the two processes is different in the α form than in the β form for samples of nearly equal overall per cent crystallinity. In both Δ and G″, the low-temperature peak decreased and the glass temperature peak increased in intensity as the fraction of β form crystallinity present increased. Data for the high-temperature relaxation (ca. 80°C) indicate a dependence upon orientation and/or crystal form in addition to a dependence upon per cent crystallinity.     

Vibrational spectra and rotational isomerism of methyl methylsilyl sulphide

Infrared and Raman spectra of methyl methylsilyl sulphide are measured for the liquid and solid states. The fundamental vibrations are assigned and the normal vibrations calculated for two possible rotational isomers about the Si-S bond. Two different solid spectra are obtained, one corresponding to the trans form and the other to the gauche form; the liquid spectrum shows the presence of both forms. The gauche form is more stable than the trans form in the liquid state by 80 ± 50 cal mol^?1. The crystallization process indicates that the freezing and melting points of the trans form are slightly higher than those of the gauche form.     

Ab initio Study of the Keto-Enol Equilibriumof Malonaldehyde

Summary.  The mechanism of the keto-enol tautomerism of malonaldehyde was studied by ab initio methods using 6-21G^** and 6-311G^** basis functions at the HF level. Two separate mechanisms were examined: through-space proton transfer in the ω-shaped form and through-space proton transfer in a sickle-shaped form obtained from the ω form by rotation. The transition state structure of the ω form is non-planar, whereas that of the sickle form is planar. The sickle form is connected with a 2^nd order saddle, indicating that there should exist a lower energy barrier, i.e. that the through-bond mechanism may be preferred. The calculated energy barriers of keto-enol tautomerism for the sickle form is twice as high as those for the omega form. Received January 18, 1999. Accepted (revised) August 4, 1999     

Mechanochemically Induced Conversion of Crystalline Benzamide Polymorphs by Seeding

Benzamide has been known for its polymorphism for almost 200 years. Three polymorphic forms are described. To date, it was only possible to crystallize a metastable form in a mixture together with the thermodynamically most stable form I. A complete transformation of form I into the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X‐ray diffraction.     

Quantification of pharmaceutical polymorphs and prediction of dissolution rate using theophylline tablet by terahertz spectroscopy

Theophylline has an anhydrous form and a monohydrated form, and the dissolution rate of the anhydrous form is higher than that of the monohydrated form. Terahertz (THz) spectra of theophylline tablet containing the theophylline anhydrous form, monohydrated form, microcrystalline cellulose and magnesium stearate exhibited a specific absorption peak at 0.96 THz, where the theophylline anhydrous form demonstrated an absorption peak. Additionally, the intensity of the peak at 0.96 THz gradually decreased as the proportion of the anhydrous form decreased. The multivariate data analysis was performed to correlate the THz spectra of theophylline tablets with the ratio of the theophylline anhydrous form. The calibration model used to predict the mixing ratio of the theophylline anhydrous form from the THz spectra achieved root-mean-squared errors of cross-validation (RMSECV) of 2.89%, a slope of 0.9934 and an R(2) of 0.9927. In addition, there were intentions to develop a prediction model for the dissolution rate of theophylline from the drug product. The dissolution rate of theophylline tablet was gradually delayed as the proportion of the anhydrous form was decreased. The multivariate data analysis was performed to correlate the THz spectra of theophylline tablets with the dissolution rate. The calibration model used to predict the percentage of theophylline dissolved in 45 min from the THz spectra achieved an RMSECV of 3.29%, a slope of 0.9260 and an R(2) of 0.9423. Furthermore, there were no significant differences between the predicted and measured percentages of theophylline dissolved in 45 min in the theophylline tablets that were stored at 84% relative humidity (RH) and 25 °C for 12 h or 3 d.     

Free energy changes by differential scanning calorimetry: Application to a low energy but metastable form of p-nitrotoluene

With decreasing sample size, a metastable form of p-nitrotoluene persists for increasing periods; for weights of 1 mg or less this form effectively supersedes the stable structure. It is unusual in having a lower enthalpy than the latter but this is offset by a lower melting point and the free energy is indeed greater than that of the stable form.     

Effects of annealing and isothermal crystallization upon crystalline forms of poly(vinylidene fluoride)

Poly(vinylidene fluoride) exists in three crystalline forms. Optimum conditions for preparing form III were established by infrared spectroscopy, differential scanning calorimetry, and x-ray diffraction measurements. Form III is easily obtained by annealing mats of solution-grown crystals of form II at 175–185°C and is also preferentially formed by isothermal crystallization from the melt between 165 and 175°C. Below 165° crystallization of form II is favored. The melting point of form III is higher than that of form II.     

Influence of molecular weight and spinning conditions on the crystalline morphology of polypropylene fibres

In the spinning of polypropylene the “smectic” phase generally appears in the as spun fibres obtained from high fluidity polypropylene (for example M̄_w = 118000) at 200°C and more. The amount of the “smectic” form decreases as the draw down ratio increases. At 200°C and for a draw ratio of 40 the “smectic” form is about 70% of the crystalline phase. At 200°C and for a draw ratio of to 130 or higher, only the monoclinic form is observed. At 180°C, and whatever is the draw ratio, only the monoclinic form is observed. For high-molecular - weight polypropylene (for example M̄_w = 320000) the “smectic” form has never been observed whatever is the spinning temperature within the range 220–260°C. The fibres with high amount of smectic phase show low orientation factors, whereas the fibres having only monoclinic form show the highest orientation factors. These results, compared with elongational behaviour of the polypropylene, suggest that the smectic form appears in the fibres as the elongation rate on the spinning line is lower than the relaxation rate of polypropylene chains.     

Studying the signaling role of 2-oxoglutaric acid using analogs that mimic the ketone and ketal forms of 2-oxoglutaric acid

2-Oxoglutaric acid (2-OG), a Krebs cycle intermediate, is a signaling molecule in many organisms. To determine which form of 2-OG, the ketone or the ketal form, is responsible for its signaling function, we have synthesized and characterized various 2-OG analogs. Only 2-methylenepentanedioic acid (2-MPA), which resembles closely the ketone form of 2-OG, is able to elicit cell responses in the cyanobacterium Anabaena by inducing nitrogen-fixing cells called heterocysts. None of the analogs mimicking the ketal form of 2-OG are able to induce heterocysts because none of them are able to interact with NtcA, a 2-OG sensor. NtcA interacts with 2-MPA and 2-OG in a similar manner, and it is necessary for heterocyst differentiation induced by 2-MPA. Therefore, it is primarily the ketone form that is responsible for the signaling role of 2-OG in Anabaena.     

Two CO binding modes for HRPCO and CCPCO: Raman evidence of CO pressure and pH dependence

Resonance Raman and infrared spectroscopy have been used to characterize the vibrational modes of CO-bound horseradish peroxidase (HRP) and cytochrome c peroxidase (CCP). At low pH both proteins show two forms attributed to linear non-H-bonded CO (form I) and tilted CO which is H-bonded with a distal residue (form II). The frequencies differ between the two proteins and indicate that H bonding is weaker for CCP. The equilibrium between the two forms depends on the CO pressure. This suggests a secondary binding to CO that perturbs the distal residue. At high pH only one form is observed. Whereas HRPCO shows form I, a new conformer, form II′, is observed for CCP. A tilted non-H-bonded CO is suggested.     

Calculation of the characteristic ratio of randomly coiled poly(L-proline).

Allowing for rotation about the Calpha-C' bond (i.e., variation of psi) and for some degree of freedom about the peptide bond (i.e., small variations of omega), the characteristic ratios, (R2)o/nl2, of the form I (cis) and form II (trans) poly(L-proline) chain have been calculated by a Monte Carlo method in which the conformational energies were used as weighting factors. The Monte Carlo method enabled short-range interactions (beyond those involved in a single residue) to be taken into account. The effect of the presence of a small amount of one form (say cis in a trans-rich chain) on (R2)o/nl2 was also investigated. The results for the trans-rich form are in good agreement with values observed experimentally in solvents in which the poly(L-proline) chain is predominantly in form II; the presence of a small amount of cis residues reduces the characteristic ratio of the trans-rich form of poly(L-proline) significantly.