Hydrolysis of Phosphorodithioates with a Seven-membered Ring( Ⅰ )——Kinetics and Mechanism of Acidic Hydrolysis

Introduction The phosphorodithioate is an important organophosphate pesticide. The hydrolysis reactions are very important to the metabolism of the pesticides. There have been many papers published in this domain concerning the hydrolysis of organophosphate esters. Studies on the hydrolysis of phosphorodithioate esters with a seven-membered ring, however, have rarely been reported. O, O-biphenyl S-alkyl phosphorothiolothionates with notable biological activities have recently been synthesized. In the present pater, UV spectroscopic method and molecular orbital calculation are used to carry out a research into the kinetics and-mechanisms of their hydrolyses.

SrCl_2 as an efficient cocatalyst for acidic hydrolysis of methyl glycosides

SrCl2 was found to be the most efficient cocatalyst for the acidic hydrolysis of methyl glycosides after 26 kinds of most representative metal salts were screened. The SrCl2-cocatalyzed acidic hydrolysis of methyl glycosides is highlighted by short reaction times, less byproducts and high yields. A possible mechanism for the SrCl2-cocatalyzed hydrolysis is also proposed.

Characterization and Selection of Microcrystalline Cellulose from Oil Palm Empty Fruit Bunches for Strengthening Hydrogel Films

Microcrystalline cellulose(MCC)is one of the cellulose derivatives produced as a result of the depolymerization of a part of cellulose to achieve high crystallinity.When implemented in other polymers,high crystallinity correlates with greater strength and stiffnes,but it can reduce the water-holding capacity.The acid concentration and hydrolysis time will affect the acquisition of crystallinity and water absorption capacity,both of which have significance as properties of hydrogel filler.The study aimed to evaluate the properties and select the MCC generated from varying the proportion of hydrochloric acid(HCl)and the appropriate hydrolysis time as a filler for film hydrogel.MCC was produced by hydrolyzing cellulose of oil palm empty fruit bunches(OPEFB)with the HCl solution at varied concentrations and periods.The results show that the longer hydrolysis times and higher HCl concentrations increase crystallinity and density while lowering yield and water absorption.The extensive acid hydrolysis reduces the amorphous area significantly,allowing the depolymerization to occur and extend the crystalline area.The morphological properties of the MCC,which are smaller but compact,indicate the presence of disintegrating and diminishing structures.A 2.5 N HCl concentration and a 45-min hydrolysis time succeed in sufficient crystallinity as well as maintaining good water absorption capacity.The treatment produced MCC with absorption capacity of 4.03±0.26 g/g,swelling capacity of 5.03±0.26 g/g,loss on drying of 1.44%±0.36,bulk and tapped density of 0.27±0.031 g/cm^(3) and 0.3±0.006 g/cm^(3),respectively,with a crystallinity index of 88.89%±4.76 and a crystallite size of 4.23±0.70 nm.The MCC generated could potentially be utilized as a hydrogel film filler,since a given proportion will be able to maintain the strength of the hydrogel,not readily dissolve but absorb water significantly.

Camalote Grass (Paspalum fasciculatum Willd) as a Sustainable Raw Material for the Production of Lignocellulosic Ethanol

The current trend of replacing a percentage of gasoline with ethanol has promoted the development of new processes for its production from lignocellulosic biomass. This work reports the production of ethanol from the Camalote grass (Paspalum fasciculatum Willd). The lignocellulosic biomass was subjected to acid hydrolysis at 125C and 15 psi with H2SO4 concentrations at 5%, 10%, and 20%, obtaining an average of reducing sugars (pentoses and hexoses) from the hydrolyzed juice with 12.3%, 10%, and 17% Brix, respectively. The sugars were fermented using yeast of the Saccharomyces cerevisiae at 30C for 48 hours. Finally, the ethanol was distilled at 78C, and the average yields were obtained through analysis of variance with a 95% confidence level. The values indicate that there is a significant difference (p > 0.05), the Tukey study shows that all the % v/v averages are different from each other. For H2SO4 concentration at 5% (10.33 ± 2), H2SO4 at 10% (9.33 ± 1.8), and H2SO4 at 20% (6.33 ± 2). The acidity analysis for the ethanol obtained from each treatment gave a value of 1.8 mg/L of acetic acid in all cases.

Isolation of Thermally Stable Cellulose Nanocrystals from Spent Coffee Grounds via Phosphoric Acid Hydrolysis

As the world's population exponentially grows,so does the need for the production of food,with cereal production growing annually from an estimated 1.0 billion to 2.5 billion tons within the last few decades.This rapid growth in food production results in an ever increasing amount of agricultural wastes,of which already occupies nearly 50%of the total landfill area.For example,is the billions of dry tons of cellulose-containing spent coffee grounds disposed in landfills annually.This paper seeks to provide a method for isolating cellulose nanocrystals(CNCs)from spent coffee grounds,in order to recycle and utilize the cellulosic waste material which would otherwise have no applications.CNCs have already been shown to have vast applications in the polymer engineering field,mainly utilized for their high strength to weight ratio for reinforcement of polymer-based nanocomposites.A successful method of purifying and hydrolyzing the spent coffee grounds in order to isolate usable CNCs was established.The CNCs were then characterized using current techniques to determine important chemical and physical properties.A few crucial properties determined were aspect ratio of 12±3,crystallinity of 74.2%,surface charge density of(48.4±6.2)mM/kg cellulose,and the ability to successfully reinforce a polymer based nanocomposite.These characteristics compare well to other literature data and common commercial sources of CNCs.

Hydrolysis of cellobiose catalyzed by zeolites—the role of acidity and micropore structure

The roles of acidity and micropore structure of zeolite were studied in the hydrolysis of the model oligosaccharide of cellulose–cellobiose. HZSM-5, HY, HMOR and Hβ zeolites were selected as model catalysts for the hydrolysis of cellobiose. The effect of acidity of zeolite, including the strength, type and location, on its catalytic activity was investigated. The strong Br？nsted acid sites located in micropores are the active sites for the hydrolysis of cellobiose to glucose. Meanwhile, the catalytic performance of zeolite is also dependent on the micropore size of zeolite.

The Crystalline Changes of Starch from Rhizoma Dioscorea by Acid Hydrolysis

The changes in crystalline properties of starch from Rhizoma Dioscorea by acid hydrolysis was characterized by X-Ray diffractometry （XRD）. The results revealed that the crystalline type of Rhizoma Dioscorea starch changed from C-type to A-type after 16 days of the acid hydrolysis. This phenomenon was different from that of other starches subjected to the acid hydrolysis. The results revealed that the B-polymorphs of C-type starch constituted the amorphous regions while the crystalline areas were mainly composed of A-polymorphs. The degree of crystallinity of the acid-thinned starch increased gradually with the time of acid hydrolysis.

Partial Hydrolysis of the Fucosylated Chondroitin Sulfate from Sea Cucumber Isostichopus badionotus and Its Mechanism

The method for preparing low molecular weight fucosylated chondroitin sulfate from sea cucumber lsostichopus badionotus using partial acid hydrolysis was reported, and its hydrolysis mechanism was also investigated. The sea cucumber chondroitin sulfate FCS was hydrolyzed under different conditions （80℃3 h and 6 h）, then isolated and purified on a Bio-P-4 geltration to prepare low molecular weight fractions （LMWF-FCS）. The chemical compositions of LMWF-FCS showed the branched fucose （Fuc） was cleaved during acid hydrolysis process, whereas the mole ratio of acetyl-galactosamine （GalNAc） and glucuronic acid （GlcA） in the backbone remained the same, which indicated the backbone was a typical chondroitin sulfate structure. The disaccharide composition analysis of LMWF-FCS suggested that the sulfation patterns of GalNAc in the backbone chain changed and the substitution value was reduced. Furthermore, the 1D NMR analysis illustrated the branched-Fuc was cleaved during acid hydrolysis, but their substitution patterns were not influenced, which was distinct from the previous reports that the substitutions of branched-Fuc in FCS were easy to change. Simultaneously, the sulfation pattern of GalNAc in backbone chain changed obviously in the acid hydrolysis process. The anticoagulant activity in vitro illuminated the anticoagulant activity of the degradation products over time in the acid hydrolysis are gradually declined, but still kept good. Therefore, the LMWF-FCS prepared could be developed as a new anticoagulant and antithrombotic drug like low molecular weight heparin.

Acetosolv delignification of marabou (Dichrostachys cinerea) wood with and without acid prehydrolysis

The chemical composition of marabou（Dichrostachys cinerea） wood and its treatment with acetic acid were investigated.Two different treatment approaches,direct acetosolv and combined acid prehydrolysis/acetosolv,were evaluated.The effects of acetic acid concentration（50%,70% and 90%） and temperature（normal boiling temperature and 121°C） on yield of solids,solubilization of lignin and hemicelluloses and recovery of cellulose were evaluated for both treatments.High solubilization of marabou components was observed in the direct acetosolv treatment at 121°C,especially at the highest acetic acid concentration,where around 84.8% of lignin and 78% of hemicelluloses were removed.When the material was subjected to acid prehydrolysis prior to acetosolv treatment,lignin solubilization was improved,especially at low acetic acid concentrations.Above 80% of the solubilized lignin was recovered from the liquors in the direct acetosolv treatment,but the recovery was lower in the combined treatment.Cellulose was well preserved in all the treatment schemes.

Hydrolysis of soy isoflavone conjugates using enzyme may underestimate isoflavone concentrations in tissue

Objective:To investigate the differences of using enzymatic hydrolysis and acid hydrolysis for identification and quantification of isoflavone aglycones from biomatrices. Methods: β-glucuronidase/sulfatase isolated from Helix pomatia for routine enzymatic hydrolysis or 6N HCl was used to release glucuronide and sulfate conjugates in the serum, urine and tissue samples. Profiles of soy isoflavones after enzymatic hydrolysis or acid hydrolysis in several tissues of rat fed with diets containing soy protein isolate were also compared using LC/MS and HPLC-ECD. Results: Acid hydrolysis released more aglycone than enzymatic digestion (P<0.05) in liver tissue. The total genistein, daidzein and other metabolites were 20% to 60% lower in samples from enzymatic hydrolysis than in acid hydrolysis. Conclusion: These results indicated that unknown factors in tissues reduced the enzymatic hydrolytic efficiency for releasing isoflavone aglycones even in optimized condition. This would underestimate isoflavone tissue concentrations up to 60%.

Study on Saccharification of Saccharum spontaneum L. by Sulphuric Acid Hydrolysis

In order to improve the saccharification rate by acid hydrolysis in the technique for production of ethanol from biomass, in this study, Saccharum spontaneum L. was used as the experimental material to investigate the rules and technological conditions for two-step acid-hydrolysis saccharification by single factor experiment and orthogonal experiment. According to the results, concentrated sulfttric acid hydrolysis was the first step, with the liquid-solid ratio of 42： 1, sulfuric acid concentration of 70%, hydrolysis time of 20 rain, and hydrolysis temperature of 55 ℃ ; dilute sulphuric acid hydrolysis was the second step, with the liquidsolid ratio of 115： 1, sulfuric acid concentration of 5.5%, hydrolysis time of 155 min, and hydrolysis temperature of 100℃. In two-step acid hydrolysis process, the yield of reducing sugar was 48.78%. The results indicated that two-step acid-hydrolysis saccharification required mild conditions, simple operation and low cost, and led to high reducing sugar yield, exhibiting a broad application prospect.

Sequence-specific Hydrolysis of Single-stranded DNA by PNA-Cerium （Ⅳ） Adduct

A novel artificial site specific cleavage reagent, with peptide nucleic acid （PNA） as sequence-recognizing moiety and cerium （IV） ions as “scissors” for cleaving target DNA, was synthesized. Subsequently, it was employed in the cleavage of target 26-mer single-stranded DNA （ssDNA）, which has 10-mer sequence complementary with PNA recognizer in the hybrids, under physiological conditions. Reversed-phase high-performance liquid chromatogram （RPHPLC） experiments indicated that the artificial site specific cleavage reagent could cleave the target DNA specifically.

Effect of Ultra-Turrax on Nanocellulose Produced by Acid Hydrolysis and Modified by Nano ZnO by Sol-Gel Method

Cellulose nanocrystals (NCC) and cellulose nanofibrils (CNF) were obtained by a single step process, with synergy between 64% sulfuric acid hydrolysis and high shear from ultra-turrax stirring, which is an advantageous process for disintegrating cellulose microcrystalline and also may improve the hydrolysis process. The surface modification on the cellulose was performed by the sol-gel process, in which the sulfate groups from hydrolysis were replaced by nanoparticles of zinc oxide, which led to the increase of up to 54&deg;C Tonset, according to thermogravimetric analysis (TGA) results. The morphology and crystallinity degree were characterized by Helium Ion Microscopy (HIM), atomic force microscopy (AFM) and X-ray diffraction. In addition, the ZnO band was observed in Fourier transform infrared spectroscopy, furthermore, the change in the zeta potential confirmed the cellulose modification. The changes in the values of proton spin-spin relaxation time for the systems showing the confined hydrogen in the rigid domains, confirmed the results observed with the aforementioned techniques, for both cellulose after hydrolysis and ZnO modified cellulose, suggesting that ZnO disrupted crystal formation in cellulose.

Isolation and characterization of Sporobolomyces sp. LF1 capable of degrading chlorimuron-ethyl

A yeast strain which was capable of degrading sulfonylurea herbicide chlorimuron-ethyl named as LF1 was isolated from a chlorimuron-ethyl contaminated soil near the warehouse of the factory producing chlorimuron-ethyl in Shenyang City, Northeast China. The strain was identified as Sporobolomyces sp., based on its morphological and physiological characteristics and the phylogenetic analysis of 18S rRNA gene sequence. So far, this is the only yeast strain of Sporobolomyces sp. which is able to degrade chlorimuronethyl. Incubation tests showed that when the initial concentration of chlorimuron-ethyl in culture was 5 mg/L, LF1 could degrade more than 77% of the herbicide after incubation for 4 d at 30℃. The possible mechanism of chlorimuron-ethyl degradation by LF1 could be the acidic hydrolysis caused by the acids from the metabolism of the yeast strain. Further study should be conducted to examine the pathways of chlorimuron-ethyl degradation by LF1 and to approach the feasibility of using LF1 to degrade the chlorimuron-ethyl in soil system.

Modification of Sugar Chains in Glycoalkaloids and Variation of Anticancer Activity

To study the effect of the sugar chains in glycoalkaloids against cancer cells, 6-0-sulfated solamargine and acidcatalyzed hydrolytic products of α-solamargine and α-solasonine were prepared. The sulfation at 0-6 of solamargine was proceeded in five steps. The 6-OH group was first selectively protected with DMT-Cl, and then the secondary hydroxyl groups on the sugar ring were acetylated. After the protective group DMTr was removed, the free 6-OH group was sulfated. Finally, the acetyl groups were removed to give 6-0-sulfated solamargine in a good yield. The hydrolyses of solamargine and solasonine were performed in diluted hydrogen chlorede. Three and two hydrolyzed products were obtained from solamargine and solasonine, respectively. The antiproliferative activities against HCT-8 tumor cells of two glycoalkaloids and their derivaties were examined via a MTT assay. The results show that α-solamargine and α-solasonine exhibit strong cytotoxic activities with an IC50 of 10. 63 and 11.97 μmol/L, respectively, wheras their derivaties seem to be less activities.

Cellulose Nanoparticles Extracted from Sugarcane Bagasse and Their Use in Biodegradable Recipients for Improving Physical Properties and Water Barrier of the Latter

The present work firstly aimed to obtain cellulose from sugarcane bagasse by using alkaline methods in pulping/delignifying and, at bleaching stages, using sodium chlorite, glacial acetic acid, and hydrogen peroxide, associated to NaOH/KOH. The process was carried out at temperatures varying from 55°C to 110°C, under magnetic stirring in various steps lasting from 2 h to 12 h. The yields of the two cellulose extracted, SCB24-Na-I and SCB24-Na-II, were 37% and 41%, respectively, from samples of ca. 15 g of the bagasse. Secondly, it is to extract nanoparticles from the obtained celluloses via acid hydrolysis (with 77% H2SO4) to lately be tested as reinforcement in biodegradable packagings. Both celluloses and their respective nanoparticles were characterized by several techniques, among them ATR-FTIR, DSC-TGA, XRD, SEM, and TEM. Despite that the yields of cellulose nanoparticles have been low, the preliminary studies of their use in biodegradable films coated on biodegradable pots were promising.

Exploring hemp seed hull biomass for an integrated C-5 biorefinery:Xylose and activated carbon

Large quantities of hemp hulls can be completely utilized for creation of value-added products (cost effective biofuels and biochemicals) through a biorefinery approach. A sustainable approach in making xylose, a low calorie sweetener and high surface area activated carbons (AC) for super capacitors, attracts interest. The AC when leveraged as a co-product from biorefinery process makes it more cost effective and, in this paper, we discuss the production of xylose and AC from hemp seed hull with methane sulphonic acid (MSA) hydrolysis. Xylose recovery with MSA hydrolysis was 25.15 g/L when compared to the traditional sulphuric acid (SA) hydrolysis of 19.96 g/L at the same acid loading of 1.8 %. The scanning electron microscope (SEM) images and Fourier transform infrared (FT-IR) spectra indicate partial delignification along with hemicellulose hydrolysis responsible for high xylose recovery. Post hydrolysis fibers were KOH activated and carbonized to make AC. The MSA hydrolyzed and KOH activated fiber produced pure, fluffier and finer particle AC with a drastic increase in surface area 1 452 m2/g when compared to SA hydrolyzed of 977 m2/g. These results indicate the potential of MSA in dilute acid hydrolysis of biomass for xylose recovery and production of high surface area activated carbon. From a production standpoint this can lead to increased use of sustainable low-cost agricultural biomass for making high surface area AC as components in supercapacitors.

Sustainable preparation and characterization of thermally stable and functional cellulose nanocrystals and nanofibrils via formic acid hydrolysis

In this work,a sustainable method to prepare functional cellulose nanocrystals(CNCs)and cellulose nanofibrils(CNFs)using formic acid(FA)(a recoverable organic acid)was established.After FA hydrolysis,the obtained CNCs could be well dispersed in DMAC.Thus,the CNC products and fibrous cellulosic solid residue(FCSR)in DMAC could be easily separated by a conventional centrifugal process,and the collected FCSR could be further fibrillated to CNFs with relatively low-intensity mechanical fibrillation process.The isolated CNC products showed high crystallinity index(about 75%)and excellent thermal stability(with onset thermal degradation temperature of 325℃).Both the resultant CNCs and CNFs showed better dispersibility in DMSO,DMF and DMAC respectively because of the introduction of ester groups on the surface of the products.The presence of surface ester groups could increase the interface compatibility of nanocelluloses with polymeric matrices and enable their applications in reinforcing polymeric matrix materials(e.g.the composite films like PHVB+CNFs).

Controlled acid hydrolysis and kinetics of flavone C-glycosides from trollflowers

Acid hydrolysis mechanisms of orientin-2＂-O-galactopyranoside（OGA）,orientin and other flavone C-glycosides in the trollflowers[Trollius chinensis Bunge） were studied in this report for the first time.Hydrolysis parameters including temperature,acidity,solvent and reaction time were comprehensively investigated.OGA could be hydrolyzed to orientin,followed by an isomerization to isoorientin via a reversible Wessely-Moser rearrangement reaction under stronger acidic conditions.A first-order kinetic model fitted the hydrolysis process of OGA well.Under the optimal hydrolysis conditions of 80 ℃,1.0 mol/L H^＋ and 7 h reaction time,about 77%OGA was transformed to orientin with no detectable isoorientin.These results could be helpful for better understanding of the acid hydrolysis kinetics of flavone C-glycosides,as well as the preparation of these valuable components under controlled acid hydrolysis conditions.

Five new terpenoids from Viburnum odoratissimum var.sessiliflorum

Five new terpenoids,including two vibsane-type diterpenoids(1,2)and three iridoid allosides(3-5),together with eight known ones,were isolated from the leaves and twigs of Viburnum odoratissimum var.sessiliflorum.Their planar structures and relative configurations were determined by spectroscopic methods,especially 2D NMR techniques.The sugar moieties of the iridoids were confirmed asβ-D-allose by GC analysis after acid hydrolysis and acetylation.The absolute configurations of neovibsanin Q(1)and dehydrovibsanol B(2)were determined by quantum chemical calculation of their theoretical electronic circular dichroism(ECD)spectra and Rh2(OCOCF_(3))_(4)-induced ECD analysis.The anti-inflammatory activities of compounds 1,3,4,and 5 were evaluated using an LPS-induced RA W264.7 cell model.Compounds 3 suppressed the release of NO in a dose-dependent manner,with an IC_(50) value of 55.64μmol·L^(-1).The cytotoxicities of compounds 1-5 on HCT-116 cells were assessed and the results showed that compounds 2 and 3 exhibited moderate inhibitory activities with IC_(50) values of 13.8 and 12.3μmol·L^(-1),respectively.