Development of nanostructure in resistant starch type III during thermal treatments and cycling

The effect of recrystallization temperature on the lamellar structure of RSIII samples was studied using XRD and SAXS. The polymorph type could be manipulated in a controlled manner, independently of the plant source. In RSIII from corn starch and from high-amylose corn starch, retrogradation at a low temperature led to the formation of polymorph B with lamellas arranged in long-range periodicity, whereas retrogradation at a high temperature led to the formation of polymorphs A and V with no defined periodicity. The retrogradation temperature of wheat starch did not have a major effect on its nanostructure. For both polymorphs, the enzymatic degradation decreased as the degree of order within the crystal increased.     

Study on the morphology, crystalline structure and thermal properties of yellow ginger starch acetates with different degrees of substitution

Yellow ginger starch acetates with different degrees of substitution (DS) were prepared by reacting native starch with glacial acetic acid/acetic anhydride using sulfuric acid as catalyst. X-ray diffraction (XRD) of acetylated starch revealed that the crystal structure of native starch was disappeared and new crystalline regions were formed. Their formation was confirmed by the presence of the carbonyl signal around 1750 cm⁻¹, as well as the reduced hydroxyl groups, in the Fourier transform infrared spectroscopy (FT-IR). The scanning electron microscopy (SEM) suggested most of the starch granules disintegrated with many visible fragments along with the increasing DS. The thermal behavior of the native starch and starch acetate were investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA), it was observed that the thermal stability of acetylated starch depends on the degree of substitution. Thermal stability of high DS acetylated starch is much better than that of the original starch when DS reached to 2.67.     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.     

New Type of Food Processing Material: The Crystal Structure and Functional Properties of Waxy and Non-Waxy Proso Millet Resistant Starches

Resistant starch (RS) is widely used in the food industry because of its ability to regulate and protect the small intestine, but their distinct effects on the structural and functional properties of waxy and non-waxy proso millet starches are not completely understood. The crystalline structure and physicochemical properties of waxy and non-waxy proso millets’ starch samples were analyzed after heat-moisture treatment (HMT). The analysis revealed significant differences between the RS of waxy and non-waxy proso millets. The crystal type of proso millets’ starch changed from type A to type B + V. The relative crystallinity of the RS of waxy proso millet was better than that of non-waxy proso millet. The gelatinization temperature and thermal stability of RS significantly increased, and the pasting temperature (PTM) of the RS of waxy proso millet was the highest. The water solubility and swelling power of the RS in proso millet decreased, and the viscoelasticity improved. The correlation between the short-range ordered structure of RS and ΔH, and gelatinization properties has a stronger correlation. This study provides practical information for improving the nutritional benefits of waxy and non-waxy proso millet in food applications.     

淀粉促进丙烯酰胺聚合机理的研究

淀粉和某些天然高分子化合物能促进丙烯酰胺的聚合,它们是丙烯酰胺聚合的共存聚合物。本文用了木薯、玉米、稻米和马铃薯淀粉进行研究,探索淀粉的团粒大小、结晶度和分子量对促进作用的影响,并选择了一些模型化合物做试验。通过这些工作,提出了淀粉促进丙烯酰胺聚合的机理。     

Influence of various starch types on PCL/starch blends anaerobic biodegradation

Research concentrated on the biodegradable capability of PCL blends with various types of starch in an anaerobic aqueous environment of mesophilic sludge from a municipal wastewater treatment plant. For blend preparation, use was made of a native starch Meritena from maize, another from Waxy – a genetically modified type of maize, as well as Gel Instant, a gelatinized starch, and an amaranth starch. Additional PCL/starch blends were prepared from the same starch types, but these were initially plasticized with glycerol. The biodegradability tests were supplemented with thermo gravimetric analysis (TGA), and differential scanning calorimetry (DSC); morphology was identified using scanning electron microscopy (SEM), plus mechanical properties were also tested. While mixtures of PCL with starches plasticized with glycerol exhibited improved mechanical properties and a higher degree of biodegradation in the anaerobic environment, mixtures of PCL with pure forms of starch were ascertained as rather resistant to the anaerobic aqueous environment. TGA and DSC analysis confirmed the removal of starch and glycerol from the PCL matrix. SEM then proved these results through the absence of starch grains in the samples following anaerobic biodegradation.     

红外光谱法研究交联淀粉的退化行为

用红外光谱研究了交联淀粉的退化过程, 结果表明, 交联淀粉具有与原淀粉大分子类似的退化过程, 即淀粉大分子临近的链段间形成双螺旋局部有序化结构, 再进一步规则地排列成结晶有序的结构. 由于交联键的限制, 交联淀粉的有序化过程相对较慢、 程度较低, 而且当交联度过高时无法形成结晶结构.     

药物控释载体醋酸酯淀粉的消化性能研究

采用生物体外(in-vitro)消化模型模拟人体消化道环境，对不同取代度的醋酸酯化木薯淀粉的消化速率进行了研究；用微生物酶对醋酸酯化木薯淀粉进行生物降解并测定各个样品的抗消化淀粉含量。结果表明醋酸酯化会增大淀粉颗粒的消化速率，但随取代度的提高消化速率呈下降趋势。同样随取代度的提高，醋酸酯化也会降低淀粉糊的消化速率。醋酸酯淀粉卡抗消化淀粉含量低于原淀粉，且取代度越高含量越低。醋酸酯化会破坏和抑制淀粉中抗消化淀粉的形成。     

Ordered structures of syndiotactic poly(methyl methacrylates) studied by a combination of infrared,Raman, and NMR spectroscopy.

The C ? O stretching vibrations in Raman and infrared spectra of poly(methyl methacrylate) (PMMA) samples of various stereoregularity in solutions and in the solid state were measured. It was found that for ordered structures of syndiotactic (s) PMMA, transition dipole coupling of ester groups in ordered s-PMMA sequences leads to a splitting of the C ? O stretching vibration into three components with wavenumbers equal in the solid state and in solution, and of different activity in Raman and infrared spectra. A comparison of the time dependences of self-aggregation of s-PMMA as measured by NMR and infrared spectroscopy indicates that the first phase of the aggregation process is detected by both methods. NMR analysis of the effect of the degree of stereoregularity on the self-aggregation of s-PMMA shows that the prerequisite for the generation of a stable ordered structure is the mutual interaction of two s-sequences of a minimum length of 9 monomer units. The experimental data obtained lead to the conclusion that, in self-aggregated s-PMMA, some of the ester groups are in close contact, with the interacting s-sequences probably forming a double helix.     

An investigation of complexes of some model tripeptides containing phenylalanine and tyrosine residues with DNA by Fourier1H NMR spectroscopy

Complexes of native and denatured DNA with model tripeptides containing phenylalanine or tyrosine residues flanked by lysine or arginine residues, respectively have been investigated by pulsed Fourier¹H NMR spectroscopy. The existence of shifts into the strong-field region of the signals of aromatic protons of the model tripeptides in the complexes both with native and with denatured DNA has been shown. Results have been obtained that indicate the possibility of the intercalation of the side chains of aromatic amino acid residues into the DNA double helix.     

纳米粒子驱动受限环境下两嵌段共聚物/均聚物混合体系的自组装行为

采用含时金兹堡-朗道理论(time-dependent ginzburg-landau theory,简称TDGL)方法研究了纳米粒子(nanoparticles,简称NPs)掺杂的两嵌段共聚物/均聚物(AB/C)共混体系在球形受限下的自组装行为.在不同球形受限条件下,两嵌段共聚物/均聚物共混体系形成了多种丰富的形貌,如双螺旋结构、单螺旋结构、层状结构和洋葱环状结构等.当在以上前3种体系中掺杂纳米粒子后,体系结构发生了很大的变化.详细研究了纳米粒子的浓度和浸润强度对以上结构的影响.研究结果表明,通过调控纳米粒子的浓度和浸润性质,该共混体系实现了双螺旋结构→层状结构,单螺旋结构→双螺旋结构,层状结构→单螺旋结构等多种取向序的转变.对于洋葱环状结构,纳米粒子的加入对体系这一结构的影响不大.     

Metal‐Helix Frameworks from Short Hybrid Peptide Foldamers

The potential of structured peptides has not been explored much in the design of metal‐organic frameworks (MOFs). This is partly due to the difficulties in obtaining stable secondary structures from the short α‐peptide sequences. Here we report the design, crystal conformations, coordination site dependent different silver coordinated frameworks of short α,γ‐hybrid peptide 12‐helices consisting of terminal pyridyl moieties and the utility of metal‐helix frameworks in the adsorption of CO₂. Upon silver ion coordination the 12‐helix terminated by the 3‐pyridyl derivatives adopted a 2:2 macrocyclic structure, while the 12‐helix terminated by the 4‐pyridyl derivatives displayed remarkable porous metal‐helix frameworks. Both head‐to‐tail intermolecular H‐bonds of the 12‐helix and metal ion coordination have played an important role in stabilizing the ordered metal‐helix frameworks. The studies described here open the door to design a new class of metal‐organic‐frameworks from peptide foldamers.     

Thermal-oxidative degradation of high-amylose corn starch

Thermal oxidation degradation of high-amylose (80 %) cornstarch has been studied using thermogravimetry analyser coupled to Fourier transform infrared spectroscopy (TG-FTIR). The linear structure of amylose provides a modal material to understand how the starch microstructure affects on the decomposition mechanisms. Kinetics of the thermal oxidation has been studied using different methods. It is found that the thermal oxidation degradation is more complex than thermal degradation, thermal oxidation degradation kinetics of the starch can be interpreted in terms of multi-step degradation mechanism, the activation energies obtain from Flynn–Wall–Ozawa (F–W–O) method and modified Coats–Redfern method are in good agreement. TG-FTIR and FTIR results confirm that the thermal oxidation mechanism of starch is a process containing long chain scission and glowing combustion.     

The role of plastic beta-hairpin and weak hydrophobic core in the stability and unfolding of a full sequence design protein

In this study, the thermal stability of a designed alpha/beta protein FSD (full sequence design) was studied by explicit solvent simulations at three moderate temperatures, 273 K, 300 K, and 330 K. The average properties of the ten trajectories at each temperature were analyzed. The thermal unfolding, as judged by backbone root-mean-square deviation and percentage of native contacts, was displayed with increased sampling outside of the native basin as the temperature was raised. The positional fluctuation of the hairpin residues was significantly higher than that of the helix residues at all three temperatures. The hairpin segment displayed certain plasticity even at 273 K. Apart from the terminal residues, the highest fluctuation was shown in the turn residues 7-9. Secondary structure analysis manifested the structural heterogeneity of the hairpin segment. It was also revealed by the simulation that the hydrophobic core was vulnerable to thermal denaturation. Consistent with the experiment, the I7Y mutation in the double mutant FSD-EY (FSD with mutations Q1E and I7Y) dramatically increased the protein stability in the simulation, suggesting that the plasticity of the hairpin can be partially compensated by a stronger hydrophobic core. As for the unfolding pathway, the breathing of the hydrophobic core and the separation of the two secondary structure elements (alpha helix and beta hairpin) was the initiation step of the unfolding. The loss of global contacts from the separation further destabilized the hairpin structure and also led to the unwinding of the helix.     

Ordered structures of stereoregular poly(methyl meth-acrylates) in solutions studied by spectroscopic methods

Three groups of problems concerning ordered structures in solutions of stereoregular poly(methyl meth-acrylates) (PMMA) were studied by spectroscopic methods: (i) Self-aggregation of syndiotactic (s) PMMA in solution was followed by means of NMR and IR spectroscopy; it has been established that double helices are formed during the initial stage of aggregation, and activation and equilibrium thermodynamic parameters (ΔH, ΔS) which characterize the transition coil–double helix in s-PMMA were determined. (ii) NMR spectroscopy has demonstrated that association in solutions of atactic PMMA proceeds via interactions of stereocomplex type (interaction between m-diads and r-tetrads). (iii) It has been found that ¹³C CP/MAS NMR spectra of crystalline forms of PMMA (prepared from aggregated solutions by solvent evaporation) conform to the double-helix structure of these systems.     

Morphology,Mechanical, and Water Barrier Properties of Carboxymethyl Rice Starch Films: Sodium Hydroxide Effect

Carboxymethyl rice starch films were prepared from carboxymethyl rice starch (CMSr) treated with sodium hydroxide (NaOH) at 10–50% w/v. The objective of this research was to determine the effect of NaOH concentrations on morphology, mechanical properties, and water barrier properties of the CMSr films. The degree of substitution (DS) and morphology of native rice starch and CMSr powders were examined. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) were used to investigate the chemical structure, crystallinity, and thermal properties of the CMSr films. As the NaOH concentrations increased, the DS of CMSr powders increased, which affected the morphology of CMSr powders; a polyhedral shape of the native rice starch was deformed. In addition, the increase in NaOH concentrations of the synthesis of CMSr resulted in an increase in water solubility, elongation at break, and water vapor permeability (WVP) of CMSr films. On the other hand, the water contact angle, melting temperature, and the tensile strength of the CMSr films decreased with increasing NaOH concentrations. However, the tensile strength of the CMSr films was relatively low. Therefore, such a property needs to be improved and the application of the developed films should be investigated in the future work.     

微波辐射对淀粉结构及性质的影响

简单地介绍了微波对淀粉的辐射作用,并综述了微波辐射对淀粉形态结构和结晶结构以及淀粉凝胶化性质、热性质等影响的国内外研究进展,如微波辐射可改变淀粉颗粒形状、结晶结构及其结晶度.微波辐射时间及辐射能等技术参数能够改变淀粉的凝胶化性质,而淀粉的含水量也是重要的影响因素.淀粉的溶解性、润胀性和吸水性都会因微波辐射而较原淀粉下降.     

Enantioselective Assembly of a Ruthenium(II) Polypyridyl Complex into a Double Helix

Evolution can increase the complexity of matter by self‐organization into helical architectures, the best example being the DNA double helix. One common aspect, apparently shared by most of these architectures, is the presence of covalent bonds within the helix backbone. Here, we report the unprecedented crystal structures of a metal complex that self‐organizes into a continuous double helical structure, assembled by non‐covalent building blocks. Built up solely by weak stacking interactions, this alternating tread stairs‐like double helical assembly mimics the DNA double helix structure. Starting from a racemic mixture in aqueous solution, the ruthenium(II) polypyridyl complex forms two polymorphic structures of a left‐handed double helical assembly of only the Λ‐enantiomer. The stacking of the helices is different in both polymorphs: a crossed woodpile structure versus a parallel columnar stacking.     

An investigation of complexes of some model tripeptides containing phenylalanine and tyrosine residues with DNA by Fourier1H NMR spectroscopy

Complexes of native and denatured DNA with model tripeptides containing phenylalanine or tyrosine residues flanked by lysine or arginine residues, respectively have been investigated by pulsed Fourier¹H NMR spectroscopy. The existence of shifts into the strong-field region of the signals of aromatic protons of the model tripeptides in the complexes both with native and with denatured DNA has been shown. Results have been obtained that indicate the possibility of the intercalation of the side chains of aromatic amino acid residues into the DNA double helix.All-Union Scientific-Research Institute of the Genetics and Breeding of Industrial Microorganisms, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 751–755, November–December, 1986.     

Comparative Study on the Structural and Physicochemical Properties of Flour and Starch from Dioscorea opposita Thunb

The objective of this work was to investigate and compare the structural and physicochemical properties of Dioscorea opposita Thunb. flour(DF), starch(DS) and purified starch(PDS). DS and PDS showed higher total starch and amylose content as compared to DF. Starch granules of DF were oval shape with rough surface while DS and PDS were relatively smooth by SEM. According to XRD measurements, FT-IR spectroscopy and 13 C CP/MAS NMR spectroscopy, all samples displayed C-type crystalline pattern, and PDS displayed the highest relative crystallinity and short-range order structure. However, DF contained the greatest content of the amorphous-phase. DF displayed the absorption peaks at 1730 and 1560 cm~(-1) related to the characteristic groups of lipid and protein using FT-IR spectroscopy. Furthermore, DF exhibited significantly higher pasting temperature while DS displayed the great peak and breakdown viscosity, as well as PDS had the highest setback and final viscosity, presumably due to the chemical composition and structural differences. DF exhibited the highest gelatinization temperature whereas PDS displayed the greatest gelatinization enthalpy. The pasting and gelatinization properties of flour and starch might be related to the relative crystallinity, short-range order structure or the interactions between starch and its associated compounds. The results allow the improvement in the manufacture of Dioscorea opposita Thunb. flour and starch with desirable pasting and gelatinization properties.