Studies on Modified Tamarind Kernel Powder. Part I: Preparation and Physicochemical Properties of Sodium Salt of Carboxymethyl Derivatives

Sodium salt of 0-carboxymethyl derivatives of tamarind kernel powder (TKP), at different levels of substitution, was prepared in iso-propanol medium. The derivatives were characterised by degree of substitution (DS), intrinsic viscosity and elution profile (GPC). Alkaline solutions, purified by alcohol precipitation showed higher intrinsic viscosity due to an alkali soluble fraction. Solution properties of the derivatives as a function of DS were found to be affected both by the substituent groups as well as by the alkali used for derivatization. Swelling power, solubility and tolerance to organic solvents of the derivatives increased with increasing carboxymethylation. The interaction properties of TKP with calcium chloride and sodium tetraborate were found to be reversed upon carboxymethylation.     

Herstellung und thermische Eigenschaften hochsubstituierter Benzylstärken

Preparation and Thermal Properties of Highly Substituted Benzyl Starch. Starch reacts in alkaline medium with benzyl chloride yielding benzyl starch with various degrees of substitution. The resulting derivatives were characterized and the influence of the reaction conditions on the degree of substitution and the yield were determined. In aqueous-alkaline medium, benzyl starch with a maximum degree of substitution of 0.9 was obtained. Under water-free conditions higher degrees of substitution are possible. The highest substitution (2.9–3.0) is found by reaction of starch dissolved in dimethylsulfoxide with sodium hydroxide and benzyl chloride. Somewhat lower degrees of substitution (2.7–2.8) can be obtained in homogeneous medium with sodium hydride and benzyl chloride in dimethylsulfoxide. In dependence on the benzyl chloride concentration, also derivatives with lower degrees of substitution can be prepared. The glass transition temperatures of benzyl derivatives of starch with degrees of substitution above 2.5 are at about 45–55°C; with decreasing degree of substitution an increase of the glass transition temperature up to about 70°C is observed. The melting range of benzyl starch was found between 150 to 180°C; at these temperatures some decomposition starts.     

Chemical Modification of Guaran Gum. Part 3: Carboxymethylation in non-Aqueous Medium

Guar gum was isolated from the seeds and subjected to modification via non-aqueous carboxymethylation. Highly substituted carboxymethyl guaran derivatives could be obtained via repeating the reaction four times, where a product of degree of substitution (D.S.) 2.07 was obtained indicating that the free hydroxyl groups of both glucose and mannose (which form the main constituents of guaran) can react with monochloro acetic acid. The modification increases the solubility of the gum in cold water, and increases the stability of its pastes to microorganisms. Pastes of these derivatives are characterized by non-Newtonian pseudoplastic behaviour regardless of their D.S. or the measuring temperature, while their apparent viscosity decreases by increasing the D.S. and/or the measuring temperature.     

非水相脂肪酶催化体系分子筛脱水机制的研究

研究了非水相脂肪酶催化体系中分子筛的脱水机制.用Karl Fisher方法测定有机溶剂中的水分含量,研究在乙腈、2-甲基-2-丙醇、2-甲基-2-丁醇三种有机溶剂中分子筛的吸水等温线;着重探讨了以乙腈作溶剂时,甘露糖、蔗糖、月桂酸等底物共存对分子筛吸水行为的影响.为非水相脂肪酶催化体系建立理论预测产物平衡转化率的数学模型提供了必要的参数.     

Properties of Low‐substituted Cationic Starch Derivatives Prepared by Different Derivatisation Processes

Cationic starch ethers prepared by the chemical reaction of starch with a quaternary ammonium reagent are commercially important derivatives. Cationic potato starch derivatives were produced under pilot‐scale conditions, employing four different principles. Wet cationisation was carried out by the slurry and paste processes, in which the cationic reagent and catalyst are added to the starch. Besides being prepared by these more commonly used processes, cationic starches were also produced by dry cationisation and by adding the cationic reagent during extrusion of starch. The cationic reagent used was 2,3‐epoxypropyltrimethylammonium chloride. Derivatives with three graded degrees of substitution (DS) between 0.03 and 0.12 were prepared by each process. The physical properties of the derivatives were analysed by the following methods: polarised light microscopy, X‐ray scattering, differential scanning calorimetry (DSC), solubility and swelling behaviour, and High‐Performance Size‐Exclusion Chromatography‐Multiangle Laser Light Scattering (HPSEC‐MALLS). The degree of substitution was determined by high resolution ¹³C‐NMR spectroscopy after hydrolysis with trifluoroacetic acid. The properties of the cationic starch derivatives were highly dependent on the derivatisation method. The granular structure of the starch was not visibly affected by the slurry process. Products from the semi‐dry reaction showed some granular damage, which was particularly evident after suspension of the granules in water. In the paste and extrusion processes, the starch granules were completely destroyed. Swelling temperatures and enthalpies can be determined only for starch derivatives that still retain a granular structure. As a result, samples from the paste and extrusion reactions exhibited no swelling endotherm in DSC. The samples from the slurry process showed a shift in the swelling temperature range towards lower temperature and a decrease in swelling enthalpy both as compared to native potato starch and also with increasing DS. Similar behaviour was found for the samples from the semi‐dry process. The swelling temperature region was comparable to that of the slurry samples for the same DS but the swelling enthalpy was distinctly lower, indicating that the granular structure of the starch was altered far more by the semi‐dry than the slurry process. Swelling in excess water and solubility were affected primarily by the cationisation process, while the influence of DS was of minor importance. The extrusion products had pronounced cold‐water solubility, the semi‐dry products showed increasing cold‐water solubility with increasing DS, the paste products were highly swollen in cold water and the slurry products were insoluble in cold water. All products were soluble in hot water but the state of dissolution was different. The molar mass distributions of the samples were determined after dissolution by pressure cooking. The different derivatisation methods resulted in characteristic molar mass distributions. The average molar mass decreased in the order slurry, semi‐dry‐, paste and extrusion process.     

Peculiarities of Starch Cationization with Glycidyltrimethylammonium Chloride

Cationic starch derivatives containing quaternary ammonium groups with high degree of substitution are prepared by reaction of starch with glycidyltrimethylammonium chloride (GTAC) in different reaction media. In aqueous solutions of GTAC along with conventional hydrolysis of epoxy groups, their interaction with chloride ions also takes place. This resulted in formation of hydroxyl ions which accelerate both the hydrolysis of GTAC epoxy groups and can act as the internal catalyst in the reaction of GTAC with starch. Therefore, even in the absence of the external catalyst, cationic starch with a high degree of substitution can be obtained. The autocatalytic reaction of GTAC with starch proceeds more rapidly at higher temperatures but with lower reaction efficiency. Both in the absence of the external catalyst and in the case when sodium alkali is used as a catalyst the reaction of starch with GTAC proceeds only when a particular quantity of “free” water is present in the system. When the NaOH as catalyst is used the reaction efficiency is about 90%. The yield of starch cationization reaction decreases when the quantity of “free” water is twice or thrice higher than required for starch modification to begin.     

Preparation of Mixed Derivatives of Carboxymethyl Starch and Determination of Substitution Degree by a New Colorimetric Method

Carboxymethyl starch (CMS) and mixed CMS-benzoate derivatives were prepared and some physical properties were estimated. A new colorimetric method for determination of the substitution degree (D. S.) of CMS derivatives by using I-acid was developed. The factors affecting the color development and stability of I-acid method were studied and the most suitable conditions for color reaction were found. The substitution degrees of prepared CMS and its mixed derivatives were determined by the I-acid method and the results were compared with those of classical methods.     

Synthesis and Characterization of low DS Succinate Derivatives of Cassava (Manihot esculenta Crantz) Starch

Succinylation of cassava starch was carried out in aqueous medium to prepare derivatives with low degree of substitution (DS) and the physicochemical properties of the products were determined. A response surface design was used for the experiment with three levels of each of the three variables viz., concentration of succinic anhydride, reaction time and pH of the reaction medium. The reaction was followed in terms of the DS of the products and reaction efficiency (RE). The degree of substitution of the derivatives varied from 0.001 to 0.022 and reaction efficiency from 2.2 to 46.8%. The DS and RE showed an adequate fit to a second order polynomial model of the variables used. Succinylation brought about increase in the swelling volume, peak viscosity and paste clarity of the starch. However, the pasting temperature and solubility did not show any significant change. The in‐vitro α‐amylase digestibility of the succinylated derivatives decreased in comparison to that of native starch and this decrease correlated with a corresponding increase in DS.     

Preparation of Long-chain Esters of Starch Using Fatty Acid Chlorides in the Absence of an Organic Solvent

An efficient method of synthesizing fatty acid esters of starch without organic solvents is described. The octanoate of starch was prepared by gelatinization of native starch with formic acid, followed by treatment with octanoyl chloride. Esterification was readily carried out under a stream of N₂ at a stirring rate of 500 min ^-1 at 25—130°C for a reaction duration of 20—120 min. Formic acid enabled esterification of starch by long-chain acyl chlorides with minimum degradation. The major factors affecting the esterification reaction were optimized. The results indicated that the octanoyl degree of substitution (DS₈) was increased with increase in fatty acid chloride concentration (from 3—12 eq. per anhydroglucose unit) and rise in temperature (25°C to 130°C). Higher octanoyl chloride concentrations and temperatures led to a reduction in yield due to acid hydrolysis of starch chains. A maximum DS₈ of 1.7 was reached after 40 min of reaction, and high concentrations of formic acid decreased the octanoyl substitution. On the other hand, higher concentration of octanoyl chloride, higher temperatures and longer reaction times increased the substitution of the long acyl chain into starch.     

Low power microwave‐assisted enzymatic esterification of starch

A series of starch esters was obtained using microwave‐assisted enzymatic transformation of starch. For the reaction hog pancreas lipase was used as a biocatalyst as well as followed acyl donors: acetic, lauric, and stearic acid. DMF and DMSO were applied as a reaction media. Experiments focused on low level microwave irradiation were compared with conventional heating of the reaction mixture. The structure of obtained starch esters was investigated by means of FTIR, analysis of substitution degree, changes in molecular parameters (M_Ws and M_Ws distributions), and microscopic studies (SEM). The spectroscopic analysis confirmed the ester bond formation. The microwave‐assisted reaction in DMF and lauric acid as an acyl donor, gave the highest degree of substitution (0.513) what followed the lowest polysaccharide degradation and maintaining the granular structure of starch. According to all the results the significant shortening in the reaction time (about 2.5 times) for microwave‐assisted reactions were observed. The influence of microwaves on esterification of starch was discussed focusing on reaction media and acyl donor type. The investigated reaction systems were demonstrated as new protocols for obtaining starch ester with higher efficiency in comparison to those known as conventional. Replacement of sophisticated derivatives including vinyl esters or acyl chlorides by simple acyl donors were shown as an additional benefit of proposed starch esterification method.     

An Aqueous Alcoholic-Alkaline Process for Cationization of Corn and Pea Starches

To develop a more efficient process for cationization of corn and pea starches, the effects of gelatinization inhibitor, type of solvent and solvent concentration, starch: water ratio, reaction temperature and 2-chloro-3-hydroxypropyltrimethylammonium chloride (CHPTAC) concentration on rate and efficiency of cationization of corn und pea starches in an aqueous alcoholic-alkaline solvent were studied during 24h of reaction time. The use of watermiscible organic solvents in the aqueous alkaline media eliminated the requirement for a gelatinization inhibitor to minimize starch swelling. The alcohol concentrations which produced high reaction efficiencies were 35-75% ethanol or 2-propanol. Optimum conditions for the reaction included 65% ethanol, 50°C and a starch:water ratio of 1:1 (w/w). The degree of substitution (DS) value increased linearly with CHPTAC concentration up to O,2M CHPTAC, but reaction efficiency (RE) decreased at the O,2M CHPTAC concentration. Cationization of starch in the aqueous alcohol solvent would be an alternative to aqueous processes because of the higher DS and reaction efficiencies that were achieved more rapidly and without the aid of other gelatinization inhibitors.     

Homogeneous Synthesis and Characteri-zation of Quaternized Cellulose Derivatives in NaOH-urea Aqueous Solutions

Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.     

Preparation of Trimethylsilyl Derivatives of Polysaccharides

Trimethylsilyl derivatives of starch, amylose, amylopectin, and glycogen have been prepared by using hexamethyldisilazane as the silylating reagent and formamide as solvent. The degree of silylation ranged from 0.9 to 2.2 and is believed to be dependent on the structure and solubility of the polysaccharide. An important property of these trimethylsilyl derivatives is their complete solubility in common organic solvents like benzene, toluene, chloroform, etc.     

响应面法优化二色补血草多糖的乙酰化工艺

采用响应面试验研究合成乙酰化二色补血草多糖的最优工艺条件,以乙酰化多糖取代度为评价指标,考察反应时间、乙酸酐与多糖的物质的量比和反应温度对乙酰化多糖取代度的影响。结果表明,通过响应面试验得到的最优工艺条件为：反应时间2.6 h、乙酸酐与多糖的物质的量比3.3∶1、反应温度65 ℃。在此条件下,二色补血草乙酰化多糖取代度为0.409。初步的抗氧化性实验表明,乙酰化后的二色补血草多糖的抗氧化性能有了明显提高。     

Multiphase decomposition of novel oxygenated organics in aqueous and organic media

Prior to the massive use of new oxygenated solvents, data on their multiphase reactivity must be obtained to assess their environmental fate and impact on water and air quality. For this, the kinetics and mechanisms of the photochemical and photocatalytic degradation of selected oxygenated solvents by common tropospheric oxidants (such as OH and ozone) must be characterized. We studied the oxidation kinetics of new oxygenated solvents as pure organic liquids and in an aqueous medium by ozone and bythe OH radical, respectively. The studied chemicals are all unsaturated compounds, having none, one, or two ether groups. The results indicate that the OH reaction proceeds atthe diffusion limit by addition to the double bond. The reactive uptake coefficients associated with the reaction initiated by ozone are of the order of 10(-3). The reactions of compounds with two double bonds are very fast and probably occur at the surface. This kinetic information demonstrates that organic solvents in an organic medium or in an aqueous droplet will be oxidized rapidly by these oxidation reactions. These reactions, however, are not significant sinks for ozone and OH radicals.     

Carboxymethyl Cocoyam Starch: Synthesis,Characterisation and Influence of Reaction Parameters

Twenty carboxymethyl starch derivatives of cocoyam starch were synthesized under different reaction conditions. The influences of sodium hydroxide concentration, sodium monochloroacetate concentration, water, type of organic solvent, reaction time and temperature were evaluated for degree of substitution (DS) and reaction efficiency (RE). The optimal ratio of moles of NaOH per mole anhydroglucose unit (AGU), n_NaOH/n_AGU was 1.62. Increases in ratio of moles of monochloroacetate (n_SMCA) to mole of AGU (n_AGU) increased the DS progressively. The ratio of water to solvent (isopropanol, IPA) in the reaction media was optimal at H₂O/IPA 0.16. Both RE and the DS increased with increase in reaction time within the studied time range (1‐4 h). Increases in temperature enhanced both reaction efficiency and DS. Among the solvents studied, an isopropanol – water medium produced the optimal result. The starch paste clarity improved remarkably after carboxymethylation. Wide angle X‐ray diffractometry revealed that starch crystallinity was reduced after carboxymethylation. ¹³C‐NMR showed peaks at δ = 180.42 ppm, 80.35 ppm, 77.77 ppm, and 71.96 ppm, which were assigned to C‐O, substituted C‐2, C‐3 and C‐6, respectively. In addition, three signals appeared at δ = 74.16 ppm, 73.42 ppm and 72.59 ppm and they were assigned to the CH₂ in the carboxylate substituents.     

微波干法制取低取代度阳离子淀粉的研究

以玉米淀粉及3-氯-2-羟丙基三甲基氯化铵(CHPTMA)为原料,NaOH为催化剂,采用微波干燥法制取可用于造纸的低取代度季铵型阳离子淀粉.考察了醚化剂用量反应时间和反应温度对取代度的影响,确定了最佳反应配方和反应条件,并对产物进行了性能检测.结果表明:微波法可大大加快醚化反应速率,缩短反应时间.     

Synthesis of Novel Water‐Soluble Aminodeoxychitin Derivatives

Eight new chitin derivatives have been synthesized via S_N2 reaction of primary and secondary amines with tosylchitin. The products were characterized using FTIR and ¹H NMR spectroscopy. A degree of substitution ˜ 1 was achieved through this process. These materials are soluble in water at room temperature, which enable their further applications in the future.     

A Study of Native and Chemically Modified Potato Starch. Part I: Analysis and Enzymic Availability in vitro

The availability of native and chemically modified potato starch to α-amylase was studied in vitro (distarch phosphate, acetylated distarch phosphate and hydroxypropyl distarch phosphate). Enzyme availability was also related to results obtained during analysis of starch and dietary fibre, The degree of substitution (DS) was determined by ¹HNMR spectroscopy and the substitution sites were evaluated by gasliquid chromatography and mass spectrometry. Substitution with acetyl- and hydroxypropyl groups reduced the availability of drum-dried starch derivatives to α-amylase. In contrast, the susceptibility of raw starch increased after introduction of hydroxypropyl groups. Cross-linking with phosphate only had but minor effects on enzyme availability. The recovery of starch during analysis depended on (a) degree of hydrolysis to glucose (b) whether or not the substitution groups were removed. The lowest yields were observed when analyzing substituted derivatives after boiling and enzymic hydrolysis (60-70%). Enzymically unavailable starch was not recovered as dietary fibre when using an enzymic gravimetric assay.     

Starch Derivatives of High Degree of Functionalization. 7. Preparation of Cationic 2‐Hydroxypropyltrimethylammonium Chloride Starches

Water‐soluble starch derivatives containing quarternary ammonium groups of high degree of substitution are prepared by reacting starch with 2,3‐epoxypropyltrimethylammonium chloride in different reaction media. The reaction was carried out in aqueous sodium hydroxide under dissolution of the product, in dimethyl sulfoxide homogeneously, and completely heterogeneously in ethanol/water. The DS values of up to 1.1 in an one‐step synthesis of the samples can be controlled by adjusting the molar ratio of cationization agent to anhydroglucose unit and are only slightly dependent on the amylose content of the starting starch material. A two‐step reaction yields products of a DS of up to 1.5. The structure of the cationic starch derivatives was confirmed by means of elemental analysis, FTIR‐ and NMR spectroscopy as well as GC‐MS.