Soy-based,tannin-modified plywood adhesives

In this research, two different types of commercial tannins, namely a hydrolysable tannin (chestnut) and a condensed flavonoid tannin (mimosa), were used to prepare two types of soy-based (soy flour (SF) and soy protein isolate) adhesives for making plywood. Thermogravimetric properties (TGA) and its derivative as function of temperature (DTG) of different soy-based adhesive were measured in the range 40°C–300°C. Thermomechanical analysis (TMA) from 25°C to 250°C was done for the different resin formulations. Duplicate three-ply laboratory plywood panels were prepared by adding 300 g/m² of the adhesives’ total resin solid content composed of SF or isolated soy protein (ISP), urea, chestnut, and mimosa tannin extracts with hexamine as hardener. Based on the results obtained, tannins can improve SF adhesion properties. The TMA showed that chestnut tannin extract appeared to react well with SF, while mimosa tannin extract appeared to react well with ISP. Matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry also showed that among other reactions, the soy protein amino acids reacted with the tannins. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannin modified adhesive.     

固化单宁大孔吸附树脂对黄芩苷吸附性能的研究

研究了通过曼尼西反应合成的单宁大孔吸附树脂对黄芩苷的静态吸附、脱附、动态吸附、吸附动力学过程。结果表明,最佳静态吸附条件为:黄芩苷初始浓度固定在45mg/L,树脂投加量为0.2g,溶液pH值控制在5.5~5.99,即控制在弱酸性条件下,吸附温度控制在35℃,静态吸附24 h;等温吸附可用Freundlic h等温方程描述;最佳静态脱附条件为:以体积分数为70%乙醇水溶液作为脱附剂,脱附温度控制在45℃,静态脱附3 h;颗粒内扩散是吸附的主控步骤,可用G E Boyd扩散方程来描述。该单宁大孔吸附树脂对黄芩苷的吸附容量达25mg/g。     

Preparation and characterization of macroporous phenol‐furfural sulfonic acid resin catalyst

The macroporous phenol‐furfural sulfonic acid resin catalyst (PFuSR) was prepared. The resin was characterized by chemical analysis, thermal analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and reactions of esterification. There exist in PFuSR different kinds of acidic groups such as ? OH, ? COOH, and ? SO₃H. The catalytic relative activity of PFuSR in the reaction of acetic acid and n‐butanol is 104 times that of macroporous polystyrene sulfonic acid resin D72. Thermal analysis showed that PFuSR did not begin to desulfonate until temperatures of 220°C were reached. The resin is suitable for use continually up to 200°C, verified by successfully performing the reaction of maleic anhydride with 2‐ethyl‐1‐hexanol to form di‐2‐ethylhexyl maleate. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1764–1769, 2001     

OPTIMIZATION OF PROCESS CONDITIONS USING RESPONSE SURFACE METHODOLOGY (RSM) FOR ETHANOL PRODUCTION FROM WASTE CASHEW APPLE JUICE BY ZYMOMONAS MOBILIS

Ethanol has been known for a long time, being perhaps the oldest product obtained through traditional biotechnology. It is an attractive, sustainable energy source for fuel additives. Based on a four-level central composite design (CCD) involving the variables substrate composition (20–100%) X₁, pH (4.5–6.5) X₂, incubation temperature (28°–36°C) X₃, and fermentation time (12–60 h) X₄, a response surface methodology (RSM) for the production of ethanol using waste cashew apple juice as substrate by Zymomonas mobilis MTCC 090 was standardized. The design contains a total of 31 experimental trials with the first 16 organized in a fractional factorial design and 25 to 31 involving the replications of the central points. Data obtained from RSM on ethanol production were subjected to the analysis of variance (ANOVA) and analyzed using a second-order polynomial equation, which resulted in the optimized process conditions of 62% (v/v) as substrate concentration, pH of 5.5, temperature of 32°C, and fermentation time of 37 h. Maximum ethanol concentration (12.64 g/L) was obtained at the optimized conditions in an anaerobic batch fermentation.     

Comparison of Chemical Compositions and Antioxidant Activities of Condensed Tannins From Different Parts of Calliandra haematocephala

In this study, the condensed tannins in 70% acetone extracts of leaf, twig, and stem bark of Calliandra haematocephala were purified by a Sephadex LH-20 column, and their structures were identified using MALDI-TOF-MS and thiolysis-HPLC-ESI-MS analyses. The results showed that the condensed tannin structures varied significantly among C. haematocephala organs. The condensed tannins from leaf were essentially of prodelphinidins, consisting mainly of (epi)gallocatechin and (epi)gallocatechin-3-O-gallate units; the condensed tannins from twig and stem bark were predominately of procyanidins, with catechin, epicatechin, and (epi)catechin-3-O-gallate as the main constitutive units for the former and epicatechin as the main constitutive unit for the latter, respectively. Furthermore, in vitro antioxidant activities of these condensed tannins were evaluated using the ABTS^·+ and FRAP methods. All of the condensed tannins exhibited stronger antioxidant activities compared to those of synthetic antioxidant BHA. For all organs, the two tested activities were found to be the highest in leaf condensed tannins, followed by that in twig condensed tannins and stem-bark condensed tannins. The results suggested that the number of hydroxyl groups on the B-ring and the level of 3-O-galloylation in condensed tannins were closely related with their antioxidant activities, and that the condensed tannins from different parts of C. haematocephala could be used as a natural additive in the food and cosmetic industries.     

Preparation of cardanol–formaldehyde resins from cashew nut shell liquid for the reinforcement of natural rubber

Natural rubber was reinforced with a high loading of a cardanol–formaldehyde resin prepared from cashew nut shell liquid. Cardanol–formaldehyde resins, both resoles and novolaks, were synthesized from cardanol, which was extracted from cashew nut shells. This was done by the condensation polymerization of cardanol and formaldehyde in the presence of base and acid catalysts. The cardanol–formaldehyde resole with the highest yield (ca. 75%) was prepared with a formaldehyde/cardanol molar ratio of 2.0 at pH 8.0 and 90°C for 8 h. The cardanol–formaldehyde novolak with the highest yield (ca. 80%) was prepared with a formaldehyde/cardanol molar ratio of 0.8 at pH 2.2 and 100°C for 7 h. Fourier transform infrared and ¹³C‐NMR were employed to characterize the chemical structures of the obtained cardanol–formaldehyde resins. The resins were compatible with natural rubber in various formulations. The cured behaviors of natural rubber blended with the cardanol–formaldehyde resole and novolak resins were investigated. The cured behaviors of cardanol–formaldehyde resole and cardanol–formaldehyde novolak samples were different, reflecting differences in their chemical reactivities. Furthermore, the incorporation of cardanol–formaldehyde resins into natural rubber provided significant improvements in mechanical properties such as the hardness, tensile strength, modulus at 100 and 300% elongation, and abrasion resistance. However, the elongation at break and compression set of the blends decreased as expected. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1997–2002, 2007     

巨尾桉单宁的提取分离及其抗菌抗氧化性能

采用超声波辅助法提取了巨尾桉叶中的单宁,大孔树脂吸附法纯化了粗提物,考察了提取物对8种常见菌种的抑制作用和对H2O2、DPPH.和.OH的清除作用。结果表明,巨尾桉单宁的提取得率为4.01%;经树脂分离纯化后单宁质量分数达到53.12%;巨尾桉单宁对除大肠杆菌外的供试菌种均有较强的抑制作用,纯化后的单宁对金黄色葡萄球菌、酵母菌和痢疾杆菌的最低抑菌质量浓度(MIC)均为1.0 g/L,对蜡状芽孢杆菌和沙门氏菌的抑制作用优于阳性对照物;粗提物、纯化物在质量浓度为0.50 g/L时对H2O2有最大清除率,分别为80.00%、89.12%,其IC50分别为0.11、0.12 g/L;抗坏血酸、粗提物和纯化物均在质量浓度为1.50 g/L时对DPPH.有最大清除率,分别为98.43%、88.97%和92.21%。在清除.OH体系中,粗提物、纯化物均在质量浓度为4.00 g/L时有最大清除率,分别为87.52%和94.32%,各试样对.OH的清除能力依次为抗坏血酸>纯化物>粗提物。     

ION-EXCHANGE RESIN–CATALYZED SYNTHESIS OF POLYOXYMETHYLENE DIMETHYL ETHERS: A PRACTICAL AND ENVIRONMENTALLY FRIENDLY WAY TO DIESEL ADDITIVE

Polyoxymethylene dimethyl ethers (PODE_n) were synthesized via the reaction between dimethoxymethane (DMM) and trioxymethylene catalyzed by CT175, a macroporous strongly acidic cation-exchange resin. The influences of reaction conditions such as catalyst types, reaction temperature, time, pressure, catalyst dosage, and mass ratio of DMM to trioxymethylene were also investigated. Under the optimized conditions of m(dimethoxymethane):m(trioxymethylene) = 2.5:1, CT175 (7.5 wt.%), 90°C, 0.5 h, and 1.5 MPa, the conversion of trioxymethylene and the selectivity to PODE_3-8 was obtained as high as 89.0% and 64.2%, respectively. Moreover, the resin catalyst can be reused up to 20 times without obvious change in its activity. The 100% atom efficiency, green reaction process, mild reaction conditions, as well as easy workup make the protocol advantageous and acceptable.     

Methods and pitfalls of extracting condensed tannins and other phenolics from plants: Insights from investigations onEucalyptus leaves

Optimal conditions for extraction of tannins and other phenolics from tree foliage and their subsequent storage rarely have been investigated. We investigated methods of drying leaves, optimal solvents, and the effects of light and temperature on the extractability and stability of condensed tannins (proanthocyanidins) and total phenolics from leaves ofEucalyptus trees. Aqueous acetone was a better solvent than aqueous methanol for condensed tannins and total phenolics, but condensed tannins were less stable in aqueous acetone than aqueous methanol. Stability of condensed tannins also was decreased substantially by room temperature versus 4°C and by exposure to indirect sunlight, although the assay for total phenolics was unaffected. For quantitative estimation of condensed tannins, extraction with 50% acetone was better than methods of direct analysis of leaf tissue. The highest estimates of total condensed tannins were obtained by exhaustive extraction with 50% acetone followed by direct analysis of the residue. Lyophilization of fresh leaf increased yield of condensed tannin (although usually by less than 10%). Lyophilization and subsequent storage of extracts had little effect on assays for condensed tannins or total phenolics.     

巨尾桉单宁的纯化工艺及其抗氧化抑菌性能

利用NKA-9大孔树脂纯化了巨尾桉树皮和树叶中的单宁,并采用二苯基苦基肼自由基(DPPH·)和羟基自由基(·OH)的清除作用评价了其抗氧化性,采用滤纸片扩散法测定了其对5种常见食源性致病菌的抑菌作用。结果表明,在上样质量浓度0.8 g/L、上样量10 mL、体积分数80%乙醇解吸液用量为3倍柱体积(BV)的动态纯化条件下,树皮单宁纯化物中单宁的质量分数为47.82%;在上样质量浓度0.5g/L、上样量10mL、体积分数80%解吸液用量3BV的动态纯化条件下,树叶单宁纯化物中单宁的质量分数为37.00%。树皮和树叶中单宁纯化物对DPPH·的半抑制浓度(IC50)分别为0.0121和0.0168g/L;当单宁质量浓度为0.6 g/L时,对·OH的清除作用相当于V_C的2.55和2.19倍。树皮和树叶中单宁纯化物对大肠杆菌、金黄色葡萄球菌、痢疾杆菌、沙门氏菌、蜡状芽孢杆菌的抑制作用均强于粗提物,且对痢疾杆菌的抑菌圈直径分别达13.25、12.50 mm。     

Interfacial encapsulation of bio‐based benzoxazines in epoxy shells for temperature triggered healing

Successful application of interfacial engineering for the preparation of cross‐linked epoxy microspheres containing thermally polymerizable cardanol‐based benzoxazine (Bz‐C) monomer in the core is demonstrated. Bz‐C is facilely synthesized by Mannich type condensation of cardanol (a by‐product of cashew nut industry) and aniline with formaldehyde under solventless conditions. The encapsulation process relies on the preferential reaction of polydimethylsiloxane immiscible epoxy resin and amine‐based hardener to form a cross‐linked spherical shell at the interface. The microcapsule dimensions and core content could be tailored by modulating the operating parameters, particularly stirring speed and Bz‐C: epoxy ratio. Spherical microcapsules with a core content of ～37% were obtained when the reaction was carried out at 600 rpm, while maintaining the reaction medium at 70°C with Bz‐C: epoxy ratio of 2.3 : 1. The simplicity and versatility of the present methodology are the forte of this technique, which widens the scope for large‐scale application of benzoxazines in the field of temperature triggered healing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42832.     

A Study on Composites from Casein Modified Melamine-Formaldehyde Resin

Amino resins are used for various applications such as decorative plastic plates, decorative wood boards, particle boards, leather tanning, foam, coating, and molding materials. In the present work, it was planned to prepare modified melamine-formaldehyde resin by incorporating casein. The intended melamine-formaldehyde-casein (MFC) resin samples were prepared under alkaline condition with an 1:3 melamine: formaldehyde ratio. Casein was incorporated in varying proportions (up to 25% w/w of melamine content) at 85–90°C. The samples were characterized by viscosity measurement and vapor pressure osmometry (VPO). The resin samples were cured isothermally at 60°C using ammonium chloride as well as hydroxylamine hydrochloride and at 120°C using hexamine as the curing agents. Jute fabric (JFRC) and glass fabric reinforced composites (GFRC) were produced by maintaining 60:40 and 40:60 proportion of resin to reinforcement materials, respectively. The laminates thus formed were characterized for their mechanical properties and chemical resistance.     

Tannin Composition Affects the Oxidative Activities of Tree Leaves

We examined whether tannin composition plays an important role in explaining the oxidative activities of tree leaves of Acer saccharum (sugar maple) and Quercus rubra (red oak). Sugar maple leaves contained substantial amounts of ellagitannins, condensed tannins, and galloyl glucoses, whereas red oak leaves contained almost exclusively condensed tannins. Oxidative activities of the crude phenolics from both species, and the phenolic fractions from sugar maple, were measured with electron paramagnetic resonance (EPR) spectrometry and UV-visible spectrophotometry. The two assays produced similar results: (1) sugar maple phenolics produced larger semiquinone radical concentrations,and higher semiquinone decay rates and browning rates than did red oak phenolics;(2) ellagitannin levels were positively associated with the three measures of oxidative activity; and (3) condensed tannin and galloyl glucose levels were negatively associated with these measures. The negative relationship between condensed tannin levels and oxidative activity resulted from the antioxidant effects of condensed tannins on hydrolyzable tannins; several purified condensed tannins significantly decreased the concentrations of semiquinone radicals and browning rates of pedunculagin (an ellagitannin) and pentagalloyl glucose. As expected, whole-leaf extracts from sugar maple produced elevated levels of semiquinone radicals, but none were observed in red oak extracts when the two species were compared with an EPR time-course assay. We conclude that the oxidative activities of tree leaves may be affected by tannin composition, and that the prooxidant activity of ellagitannins may be decreased by co-occurring condensed tannins.     

Biochemical responses of Pinus pinaster trees to fire-induced trunk girdling and crown scorch: secondary metabolites and pigments as needle chemical indicators

The biochemical responses to varying levels of localized heat damage to stems and crowns were studied in Pinus pinaster trees in Galicia, Spain. The objective was to ascertain the utility of secondary metabolites (total polyphenols, condensed tannins, astringency, free and esterified phenolic acids) and pigments (chlorophylls and carotenoids) as chemical indicators of localized fire damage. The study involved three levels of girdling by trunk heating (0%, 60%, and 75%), three levels of crown scorching (0%, 50%, and 75%), and all combinations of those trunk and crown treatment levels. Secondary metabolites and pigments were analyzed in needles before, during, and up to 8 months after fire treatments. High levels of polyphenols, condensed tannin, and pigments occurred in situations where the sole treatment was 75% crown scorching. Low levels of hydroxycinnamic acids were the result when the treatment was 75% trunk girdling. These responses occurred in the first two months after fire. Thereafter, normal values were observed. Low values of chlorophyll a/b ratio and high levels of free protocatechuic and esterified syringic acids were found to be long-term indicators of trunk girdling damage combined with crown scorching.     

大孔磺酸树脂催化合成7-羟基-4-甲基香豆素

考察了DT-852大孔磺酸树脂催化合成7-羟基-4-甲基香豆素的工艺。结果表明,DT-852大孔磺酸树脂具有较好的催化活性;7-羟基-4-甲基香豆素较佳的合成工艺为:反应温度105℃,反应时间2.5h,催化剂用量1.0g,物料比n(乙酰乙酸乙酯)∶n(间苯二酚)=1∶1,产率为93.8%,w(7-羟基-4-甲基香豆素)=98.3%(HPLC),催化剂可重复使用多次。产物结构经FTIR验证。     

Glycerolysis of Buriti Oil (Mauritia flexuosa) by Magnesium Oxide and Immobilized Lipase Catalysts: Reaction Yield and Carotenoids Degradation

Buriti (Mauritia flexuosa) is a palm tree widely distributed in South America. The oil extracted from its fruit is an added value product for its high carotenoids content. The aim of this work was to evaluate the alkaline (magnesium oxide—MgO) and enzymatic (lipase B from Candida antarctica immobilized on macroporous acrylic resin) glycerolysis of buriti oil to obtain non-ionic emulsifiers and evaluate the carotenoids degradation during this process. Alkaline glycerolysis was carried out using a 3:1 glycerol/oil molar ratio, temperatures of 170 and 210 °C, and MgO contents of 0.5 and 1%wt. Enzymatic glycerolysis reactions were performed using 3%wt. of a lipase catalyst and varying the following parameters: glycerol: oil molar ratio (3:1, 6:1, and 9:1), solvent (tert-butyl alcohol) concentration (50%, 150%, and 250%, vol./substrate mass), and temperature (40, 55 and 70 °C). The products were analyzed by liquid chromatography and UV–visible spectroscopy (370–520 nm). Enzymatic glycerolysis was superior in terms of conversion and selectivity to monoacylglycerols (MAG). MAG yields were close to 80% or higher for most conditions tested for enzymatic glycerolysis, while the maximum yield for alkaline glycerolysis was of 58%. UV–Vis data showed that carotenoids were severally degraded in alkaline glycerolysis, while the enzymatic product exhibited high preservation of carotenoids and color and odor similar to those of the pure buriti oil. Based on the final composition of the non-ionic emulsifiers obtained from buriti oil by enzymatic glycerolysis, they can be considered potential raw materials for cosmetic and food industries.     

Characterization and antioxidative properties of condensed tannins from the mangrove plant Aegiceras corniculatum

Freeze‐dried leaf, stem bark, and root bark powders of Aegiceras corniculatum were extracted with three different types of polar solvents: methanol, ethyl acetate, and water. The methanol extracts had the highest concentrations in total phenolics and extractable condensed tannins, followed by water and ethyl acetate extracts. Analysis by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) suggested that condensed tannins from leaf, stem bark, and root bark contained prodelphinidins and procyanidins, with the predominance of prodelphinidins and high level of galloylation. Acid‐catalyzed degradation in the presence of benzyl mercaptan indicated that gallocatechin, epigallocatechin, epigallocatechin‐3‐O‐gallate, and epicatechin‐3‐O‐gallate occurred as the terminal units and (epi)gallocatechin, (epi)gallocatechin‐3‐O‐gallate, (epi)catechin, and (epi)catechin‐3‐O‐gallate occurred as the extension units. The mean degrees of polymerization (mDP) of condensed tannins from leaf, stem bark, and root bark were 13.5, 7.4, and 12.3, respectively. The condensed tannins from leaf and stem bark exhibited a higher DPPH radical scavenging activity and ferric reducing/antioxidant power compared to that of synthetic antioxidant butylated hydroxyanisole (BHA). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Optimization of Sulforaphane Separation from Broccoli Seeds by Macroporous Resins

Abstract

In this study, the adsorption and desorption properties of sulforaphane on macroporous resins (HP20, SP207, SP850, and HP2MGL) were investigated. Analysis revealed that SP850 resin was most effective in the separation of sulforaphane. The equilibrium experimental data obtained at different temperatures were well fitted to the Langmuir and Freundlich isotherms. To optimize the separation process, dynamic adsorption and desorption tests were performed with a column packed with SP850 resin. The results showed that the optimum parameters for adsorption were as follows: flow rate: 5 BV/h, pH 2, temperature: 25°C; for desorption: ethanol–water (40:60, v/v), 6 BV as an eluent, flow rate: 6 BV/h. The highest purity of sulforaphane product was 85.9%, i.e., 107‐fold higher than those in broccoli seeds through one run treatment on the column packed with SP850 resin under normal conditions. This indicated the high efficiency of SP850 resin in separating sulforaphane.     

Hybrid Polymer Networks of Epoxy Resin and Substituted Phenolic Novolacs

Hybrid polymer networks of diglycidyl ether of bisphenol (DGEBA) resin and phenolic novolac resins were prepared and tested for mechanical properties, hardness, and water absorption. The novolacs employed were based on each of phenol and substituted phenols such as p-cresol, t-butyl phenol, and cardanol. Cardanol is the main constituent of cashew nut shell liquid (CNSL), a renewable resource. Blends containing 10–15 wt% of novolac resin show substantial improvement in properties. These properties show a declining trend with higher novolac loading. The stoichiometric ratio between phenol and formaldehyde in the novolacs was optimized (1:0.8) for maximum property enhancement. The property profiles of the epoxy/novolac networks show that novolacs are effective modifiers for commercial epoxy resin. Incorporation of novolacs of substituted phenols results in relatively greater improvement in energy absorption during failure.     

葡萄柚精油中抗癌成分橙油素的分离及鉴定

橙油素是广泛存在于柑橘类果实中的天然抗癌活性成分.选用SP70大孔吸附树脂分离纯化葡萄柚精油中的橙油素,该树脂对于橙油素的吸附容量和解吸率分别达到14.53 mg/g和83.32％,并成功地从树脂床层的洗脱液中结晶分离出橙油素晶体.对所得晶体分别采用差示扫描量热仪(DSC)、紫外吸收光谱(UV)、红外吸收光谱(IR)、...