Synthesis of Cellulose-graft-Polychloromethylstyrene-graft-Polyacrylonitrile Terpolymer/Organoclay Bionanocomposite by Metal Catalyzed Living Radical Polymerization and Solvent Blending Method

A bionanocomposite of grafted cellulose and organo-modified clay was synthesized through solution intercalation method. For this purpose, chloromethylstyrene was grafted onto cellulose using acryloylchloride and the subsequent free radical polymerization. The synthesized cellulose-graft-polychloromethylstyrene was used as an atom transfer radical polymerization macroinitiator of acrylonitrile in the presence of CuCl/2,2′-bipyridine catalyst system, to prepare the cellulose-graft-polychloromethylstyrene-graft-polyacrylonitrile terpolymer. For preparing the modified clay, Na-montmorillonite was mixed with hexadecyl trimethyl ammonium chloride salt. Finally, cellulose-graft-polychloromethylstyrene-graft-polyacrylonitrile/organoclay bionanocomposite was prepared in CCl₄ by solution intercalation method.     

Construction of Cellulose Binding Domain Fusion FMN-Dependent NADH-Azoreductase and Glucose 1-Dehydrogenase for the Development of Flow Injection Analysis with Fusion Enzymes Immobilized on Cellulose

The cellulose binding domain (CBD) of cellulosome-integrating protein A from Clostridium thermocellum NBRC 103400 was genetically fused to FMN-dependent NADH-azoreductase (AZR) and glucose 1-dehydrogenase (GDH) from Bacillus subtilis. The fusion enzymes, AZR-CBD and CBD-GDH, were expressed in Escherichia coli Rosetta-gami B (DE3). The enzymes were purified from cell-free extracts, and the specific activity of AZR-CBD was 15.1 U/mg and that of CBD-GDH was 22.6 U/mg. AZR-CBD and CBD-GDH bound strongly to 0.5 % swollen cellulose at approximately 95 and 98 % of the initial protein amounts, respectively. After immobilization onto the swollen cellulose, AZR-CBD and CBD-GDH retained their catalytic activity. Both enzymes bound weakly to 0.5 % microcrystalline cellulose, but the addition of a high concentration of microcrystalline cellulose (10 %) improved the binding rate of both enzymes. A reactor for flow injection analysis was filled with microcrystalline cellulose-immobilized AZR-CBD and CBD-GDH. This flow injection analysis system was successfully applied for the determination of glucose, and a linear calibration curve was observed in the range of approximately 0.16–2.5 mM glucose, with a correlation coefficient, r, of 0.998.     

二醋酸纤维素薄膜剂量计的制备和性能研究

为了改善醋酸纤维素薄膜剂量计在γ辐射剂量测定中稳定性欠佳的问题，拓展其辐射测量应用范围，采用离子液体均相乙酰化纤维素方法制得的二醋酸纤维素（CDA）粉末为原料，优化CDA薄膜制备工艺，研究其γ辐射变色性能及稳定性，制备适用于γ辐射剂量测量且性能优良的CDA薄膜剂量计。基于CDA的辐射变色机理，该薄膜剂量计在270 nm的单位厚度吸光度与吸收剂量存在良好的线性关系，剂量率、CDA的取代度和辐照气氛对薄膜的工作曲线影响较小。CDA薄膜剂量计的剂量检测量程为50~400 kGy，扩展不确定度为8.8%（K=2），辐照后24 h内吸光度测试稳定，具有良好的辐照稳定性，基本满足工业上对于辐射剂量计的使用要求，有望应用于γ辐射剂量的测量。     

Synthesis and testing of cellulose acetate nicotinate as adsorbent for rhodamine B dye

The esterification of cellulose hydroxyl groups with natural carboxylic acids in mild conditions represents an adequate pathway in obtaining cellulose derivatives with different useful properties. In this article, authors report the synthesis of new mixed ester of cellulose and cellulose acetate nicotinate (CAN) , in a homogenous medium using DMF as solvent, cellulose acetate (CA) as starting cellulosic material, and nicotinic acid as an esterification agent in the presence of p-toluenesulfonyl chloride and pyridine. FTIR and NMR techniques were used to prove the binding of nicotinoyl group at free hydroxyl groups of CA. The obtained CAN was electrospun by electrospinning technique to obtain adsorbent ultrafine fibers, evidenced by SEM images, with high specific surface area. Monolayer Langmuir and empirical Leundrich isotherms were used to assess the adsorption capacity for rhodamine B dye of electrospun CAN in comparison with that of electrospun CA used as starting material. Langmuir isotherm led to a better assessment of experimental data suggesting that the adsorption is mainly determined by hydrogen bonds formed between carboxylic OH hydrogen bonding donor and pyridine N hydrogen bonding acceptor. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47772.     

Study of Load Capacity of Avicel PH-200 and Cellactose,Two Direct Compression Excipients,Using Experimental Design

The load capacity of two excipients, a large particle size grade of microcrystalline cellulose (Avicel? PH-200) and a coprocessed material composed of lactose and pulverized cellulose (Cellactose?) was determined using a model mix with Dipyrone (metamizol sodium) and experiments planned by design of experiments. A multiple-regression model was proposed, and as a result, a new parameter, called specific load capacity S_LC was obtained. This constant can be determined for other excipients and drugs; it depends only on the excipient and the drug used.     

Peroxidation of Polymethylhydrogensiloxane and Cellulose by γ-Irradiation in Air and Grafting Induced by Their Decomposition

The peroxides of polymethylhydrogensiloxane, cellulose and a mixture of both were determined by ferrous ion method. The relation between the decomposition of the peroxide and the degree of grafting by standing at an elevated temperature after irradiation was examined.

The G-value for the peroxide formation of polymethylhydrogensiloxane was found to be 8.7, and the activation energy for the peroxide decomposition was determined from calculation to be 43 kcal/mol. The ratio of G-values of silicone between those terminated by methyl radical and by methyl radical is estimated to be about 2/1. It would thus appear certain that the rate of peroxidation is affected by the end group. The peroxidation is not a chain reaction at room temperature, and the peroxide is produced by the recombination of the peroxy radical. At least two types of peroxide are produced by irradiation in air, and one is decomposed at 80°C but the other is relatively stable.

On the other hand, the G-value for the peroxide formation of cellulose is equal to 5.6.

The tendency seen for the decrease of the peroxide corresponds to that of increasing degree of grafting, and it may be concluded that only 1/10 of the peroxides formed in the cellulose–silicone system results in grafting, since it has been calculated that the G-value for the grafting through the peroxide is about 1.0.     

In vitro release of ketoprofen from hydrophilic matrix tablets containing cellulose polymer mixtures

The effect of cellulose ether polymer mixtures, containing both hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC K15M or K100M), on ketoprofen (KTP) release from matrix tablets was investigated. In order to evaluate the compatibility between the matrix components, Raman spectroscopy, scanning electron microscopy (SEM), and X-ray powder diffraction (XRPD) experiments were performed. The results evidence the absence of significant intermolecular interactions that could eventually lead to an incompatibility between the drug and the different excipients. Formulations containing mixtures of polymers with both low and high viscosity grades were prepared by a direct compression method, by varying the polymer/polymer (w/w) ratio while keeping the drug amount incorporated in the solid dispersion constant (200?mg). The hardness values of different matrices were found within the range 113.8 to 154.9 N. HPLC analysis showed a drug content recovery between 99.3 and 102.1%, indicating that no KTP degradation occurred during the preparation process. All formulations attained a high hydration degree after the first hour, which is essential to allow the gel layer formation prior to tablet dissolution. Independent-model dissolution parameters such as t_10% and t_50% dissolution times, dissolution efficiency (DE), mean dissolution time (MDT), and area under curve (AUC) were calculated for all formulations. Zero-order, first-order, Higuchi, and Korsmeyer–Peppas kinetic models were employed to interpret the dissolution profiles: a predominantly Fickian diffusion release mechanism was obtained – with Korsmeyer–Peppas exponent values ranging from 0.216 to 0.555. The incorporation of HPC was thus found to play an essential role as a release modifier from HPMC containing tablets.     

Surrogate functionality of celluloses as tablet excipients

Background: The variety of excipients from different sources and prices to which we have access gives rise to the necessity to evaluate their functional characteristics. The aim of this work is to determine some physical and technological characteristics of celluloses from different sources, India and United States, to ascertain their functionality as tablet excipients. Methods: The used surrogate functionality properties are particle morphology and particle size distribution, compactibility, ejection pressure, and the disintegration properties of pure excipients and their compressed tablets. Results: The innovators Avicel and Croscarmellose show advantages over the generic celluloses Alfacel and Carmacel. Avicel PH 101 and 102 show an average of 26% greater compactibility than both types of Alfacel, whereas the compactibility of Croscarmellose is greater than that of Carmacel in about 50%. Avicel tablets compacted at a compaction pressure of 47 MPa exhibit shorter disintegration times (3.7 minutes) than Alfacel tablets (28 minutes), whereas Carmacel show better disintegrant properties than Croscarmellose. This occurs regardless of the similar particle morphology, size, and size distribution. As expected, all celluloses show low ejection pressures. Conclusion: The surrogate functionality properties of the generic celluloses are still considered as satisfactory to be used as tablet excipients, although they are inferior in some aspects to innovator celluloses. Alfacel and Carmacel have the potential to be used as filler, binder, and disintegrant, in the design of tablets. Moreover, one should bear in mind that the differences reported here may be altered because of a possible inter-batch variability and variations in the moisture content.