A new method for determination of hydroperoxides in cellulose

A new chromatographic method for determination of hydroperoxides in cellulose is described, whereby the sample is dispersed in phosphate buffer solution (pH 7) of FeCl(3), EDTA and the hydroxyl radical scavenger, N,N'-(5-nitro,1,3-phenylene)bisglutaramide. The reaction time, concentration of reagents and chromatographic conditions for subsequent separation and quantification of hydroxylated products are optimised. The limit of detection is 0.14 micro mol L(-1) H(2)O(2) which corresponds to 2.1 micro mol hydroperoxides per kg of cellulose (mass of sample: 0.4 g). It was shown that in the concentration range of H(2)O(2) up to 15 micro mol L(-1) the method gives linear response and that adsorption of reaction products on fibres is negligible. For cellulose samples, this corresponds to a linear range of 2.1-225 micro mol of hydroperoxides per kg. Due to possible side reactions of hydroxyl radicals in the suspension of analyte, it is recommended that the standard addition technique is used. In purified cotton cellulose, the steady state concentration of hydroperoxides at room conditions was found to be 15.1+/-1.5 micro mol kg(-1).     

Effects of drying and pressing on the pore structure in the cellulose fibre wall studied by 1H and 2H NMR relaxation

A 1H and 2H NMR relaxation method was used to investigate the influence of drying and pressing on the pore size and pore size distribution in the cellulose fibre wall. The investigation was made in the moisture interval in which cellulose fibres normally shrink, i.e. from a moisture ratio of about 1.5 g water/g fibre to dry fibres. When the moisture content of a fibre sample was decreased by drying or pressing, the pores decreased in size and the pore size distribution became narrower. It was found that there were only small differences at a given moisture content between the pore size distributions of samples prepared by drying and by pressing. The results also indicate that the pore shrinkage in cellulose fibres during pressing or drying is a process in which the cell wall pores of a wet cellulose fibre successively shrink as the moisture content decreases. It was observed that, at low moisture contents, pressing and drying resulted in different 1H NMR spin-lattice relaxation profiles. This is discussed in terms of morphology differences in the fibre matrix. The mobility of the protons in the solid phase influences the liquid 1H NMR spin-lattice relaxation in heterogeneous systems through magnetization transfer. We have also studied the effects of hornification in recycled pulps     

A new method of evaluating the average electro-osmotic velocity in microchannels

A new and simple method to evaluate the average electro-osmotic flow velocity in microchannels is presented in this paper. In this method, the average electro-osmotic flow velocity is determined by using the slope of the measured current-time relationship during the electro-osmotic flow of one solution replacing another similar solution. The two solutions have the same electrolyte and a small difference in ionic concentration. Careful experiments were conducted to measure the electrical current change with time during such a displacing process under a constant applied electrical field. KCl and LaCl3 electrolyte solutions and 10-cm-long polyamide-coated silica capillary tubes of 100 and 200 microm in internal diameter were used in this study. The average velocities were determined by using the slope method. A numerical model was also developed to predict the average velocity of such an electro-osmotic flow. An excellent agreement in the average velocities between the slope method and the model predictions was found.     

A new method for measuring the diffusion coefficient in a gas phase

A new and fast method for measuring the diffusion coefficients of binary gas mixtures using ion mobility spectrometry (IMS) has been developed. In this method, the sample is injected as a short pulse into the flowing drift gas, forming a Gaussian concentration profile inside the drift region. This Gaussian cloud is irradiated with a fast moving swarm of electrons to create negative ions. The flash of electrons is so short that the negative ions do not move much during the exposure time. The ions then drift toward the detector, where they are collected. The collected ion signal pattern reflects the spatial distribution of the sample inside the cloud at the time of exposure. This is repeated in intervals of 300-400 ms to monitor the spatial spreading of the molecules in the drift region. Consecutive IMS spectra show the evolution of the cloud over time. The collected spectra are fit to Gaussian functions to extract diffusion coefficients. Using this method, the diffusion coefficient of O(2), CHCl(3), and C(2)H(2)Cl(2) were measured, and the results are in good agreement with the previously reported experimental data.     

Near-infrared spectrum of cellulose: A new method for obtaining crystallinity ratios

Absorption bands in the near-infrared (NIR) spectrum of cellulose were correlated with crystalline and noncrystalline regions and used to derive a new crystallinity ratio. NIR crystallinity ratios of both natural and regenerated celluloses were measured and compared with x-ray diffraction values. The data indicates that the NIR crystallinity ratio may also depend upon crystallite size.     

A new routine method for determination of iodine in plant materials

A new method is suggested for determination of iodine in grass and crop samples. The sample is decomposed with sulphuric, nitric and perchloric acids. Iodine is determined in the diluted digest. The method is excellent for routine work, being faster and simpler than previous nethods.     

A robust,field-deployable method for the electrodeposition of actinides

Several methods for the electrodeposition of actinides for alpha-spectrometry analysis have been developed over the past few decades, but none have been specifically designed to facilitate rapid analysis in a field situation. This paper describes the development of an electrodeposition procedure that is specifically adapted for use in a mobile lab. Using these techniques one would be able to obtain preliminary results in the event of a radiological incident. Quantitative yields with associated uncertainties have been determined for the procedure. It has also been shown that short deposition times can provide quantitative results.     

A new method for cellulose membrane fabrication and the determination of its characteristics

A novel method to fabricate semipermeable cellulose membranes based on cellulose regeneration of a dry membrane cast by the neutralization reaction is presented in this paper. In this method, an environmentally acceptable cellulose dissolution procedure is employed to prepare the membrane casting solution comprised of microcrystalline cellulose dissolved in aqueous NaOH. Moreover, a new cast drying/cellulose regeneration technique is proposed and successfully applied to prepare membranes after the exploitation of the conventional immersion precipitation method, which results in the formation of granular cellulose particles rather than membranes due to the low cellulose concentration (<5 wt%) in the cast. In the present technique, the cellulose concentration in the membrane cast is dramatically increased through water evaporation, and glycerin is utilized in the cellulose regeneration process to achieve a gentle neutralization reaction. As a result, defect-free membranes with a uniform structure are developed. A detailed investigation is also presented concerning the effects of membrane forming parameters, i.e., the concentrations of cellulose, solvent, and acid, and the membrane thickness, on membrane properties. In addition, by coordinating the molecular separation experiments via the ultrafiltration process against a number of macromolecules with various molecular weights, the fabricated membranes are demonstrated to be capable of sieving molecules with a MW above 50,000.     

A new method for the evaluation of biodegradable plastic using coated cellulose paper

A highly sensitive analytical method for evaluation of poly(L-lactide) (PLA), poly(epsilon-caprolactone) (PCL), poly(beta-hydroxybutyrate) (PHB), and poly(butylene succinate) (PBS) degradability was developed using coated cellulose paper, prepared by penetration and adhesion of these plastics into/onto the cellulose paper. Enzymatic degradability of the obtained plastic coated papers was evaluated using various commercial proteases and lipases. PLA coated paper was highly susceptible to subtilisin and mammalian enzymes, alpha-chymotrypsin, elastase and trypsin. To our knowledge, this is the first report on the degradation of PLA coated paper using subtilisin and mammalian enzymes. Almost all lipase preparations degraded PCL and PHB coated papers but not PBS coated paper. The biodegradability of plastic coated paper was greater than that of plastic powder. The penetration of plastic into cellulose paper by coating improved the plastic degradability, and can be regulated easily.     

Effects of mechanical stretching on average orientation of cellulose and pectin in onion epidermis cell wall: A polarized FT-IR study

The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm^?1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (ν_C=O, 1745 cm^?1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm^?1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development.     

A new method for measuring the induction period of the oxidation of polymers

A simple method independent of oxygen absorption measurements was developed for estimating the induction period of the oxidation of polymers. The principle of this method is the estimation of the time in which a sample oxidized at constant temperature exhibits a temperature rise as a consequence of the exothermal effect of the oxidation reaction. The temperature rise is measured as the temperature difference between the sample and a reference material. Results of measurements of induction periods of the oxidation of polymeric substrates inhibited by various antioxidants, obtained both from oxygen absorption measurements and by the new method, are discussed.

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Zusammenfassung Eine von der Sauerstoffabsorption unabhängige Methode wurde zur Messung der Induktionsperiode der Oxydation von Polymeren entwickelt. Sie beruht auf Bestimmung der Zeit, die von einer isothermisch oxydierten Probe erforderlich ist, um einen durch den exothermischen Effekt der Oxydation hervorgerufenen Temperaturanstieg zu zeigen. Der Temperaturanstieg wird als eine Temperaturdifferenz zwischen Probe und Referenzstoff gemessen. Die Ergebnisse von Bestimmungen der durch verschiedene Antioxydanten inhibierten Induktionsperioden von Polymersubstraten durch Sauerstoffabsorption und durch die neue Methode werden besprochen.

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Résumé On développe une méthode simple et indépendante de la mesure de l'absorption de l'oxygène pour estimer la période d'induction au cours de l'oxydation des polymères. Le principe repose sur l'évaluation du temps pendant lequel un échantillon traité en conditions isothermes manifeste une élévation de température par suite de l'effet exothermique dû à l'oxidation. On mesure l'élévation de température sous forme d'une signal différentiel entre l'échantillon et une substance de référence. On discute les résultats des mesures des périodes d'induction des substrats polymères traités par divers antioxydants, en opérant à l'aide de la nouvelle méthode et par absorption d'oxygène.

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Partial Carbamoylation of Cellulose Microspheres:a New Method to Prepare Adsorbents for Liquid Chromatography简

Micron-sized cellulose microspheres were prepared through sol-gel method using NaOH/urea solution to dissolve cellulose, then cross-linked by 1,6-hexanylene diisocyanate （HDI）, toluene 2,4-diisocyanate （TDI） and 1,4-phenylene diisocyanate （PDI）, respectively. The reaction conditions for partial modification of the microspheres were studied. The degree of substitution （DS） in cellulose was controlled by adjusting the reaction conditions. HDI-crosslinked microspheres were partially modified with phenyl isocyanate to obtain chiral stationary phases （CSPs）. The CSPs of a lower degree of crosslinking （DC） showed better chiral recognition ability than those of a higher DC. Meanwhile the CSPs prepared by pre- modification exhibited better chiral recognition ability than those prepared by pre-crosslinking.     

A method for the estimation of pore anisotropy in porous solids

In this work a method for the estimation of pore anisotropy, b, in porous solids is suggested. The methodology is based on the pore size distribution and the surface area distribution, both calculated from trivial N2 adsorption-desorption isotherms. The materials used for testing the method were six MCM-Alx solids in which the ordered pore structure (for x = 0) was gradually destroyed by the introduction of Al atoms (x = 5, 10, 15, 20, 50) into the solids. Additionally, four silicas having random porosity were examined, in which the surface of the parent material SiO2 (pure silica) was gradually functionalized with organosilicate groups of various lengths (triple bond Si-H, triple bond Si-CH2OH, triple bond Si-(CH2)3OH) in order to block a variable amount of pores. As pore anisotropy, the ratio bi = Li/Di is defined where Li and Di are the length and the diameter of each group of pores i filled at a particular partial pressure (Pi/P0). The ratio of the surface area Si over the pore volume Vi, at each particular pressure (Pi/P0), is then expressed as Si3/Vi2 = 16 pi Nibi = 16 pi lambdai, where Nibi is the number of pores having anisotropy bi which are filled at each pressure (Pi/P0) and lambdai is the total anisotropy of all the pores Ni belonging to the group i of pores. Then plot of lambdai vs (Pi/P0) provides a clear picture of the variation of the total pore anisotropy lambdai as the partial pressure (Pi/P0) increases. For the functionalized silicas there appears a continuous drop of lambdai as partial pressure (Pi/P0) increases, a fact indicating that both Ni) and bi are continuously diminished. In contrast, for the MCM-Alx materials a sudden kink of lambdai appears at the partial pressure where the well-defined mesopores are filled up, a fact indicating that at this point Ni and/or bi is large. The kink disappears as the ordered porosity is destroyed by increasing the x doping in MCM-Alx. The pore anisotropy bi of each group i of pores is then estimated using the expression (Si3/Vi2) = 8 pi NiriSi and plotting log(lambdai) vs log ri. From those plots, the values of si can be found and therefore the values of bi = 0.5riSi are next defined. In the MCM-Alx materials the maximum pore anisotropy b is very high (bi approximately 250) for x = 0. Then as mesoporosity is destroyed by increasing x, the maximum b values drop gradually to b approximately 11 (x = 5), b approximately 8 (x = 10), and b approximately 3 (x = 15). For x = 20 and x = 50, the maximum b obtains values equal to unity. The same phenomena, although less profound, are also observed for the functionalized silicas, where the anisotropy b is altered by the process of functionalization and from bi approximately 0.5 for the nonfunctionalized or bi approximately 0.9 for the solid functionalized with Si-H groups drops to b = 0.3 and b = 0.2 for the solid functionalized with triple bond Si-(CH2)OH and triple bond Si-(CH2)3OH, respectively. A correlation factor F is suggested in cases where the pore model departs from the cylindrical geometry.     

A diffusion method for determining sizes of nanoparticles suspended in a gas

The diffusion deposition of particles suspended in a gas in diffusion batteries composed of cylindrical fibers is considered. It is assumed that the particle-size spectrum is described by a lognormal distribution. It is shown in the asymptotic approximation that the dependences of the penetration coefficients on the diffusion battery parameters and flow velocity plotted for particles with the same geometrical mean sizes, but different degrees of polydispersity, in fact intersect at the same point. It is also shown that, at small nanoparticle size r (on the order of several nanometers), when the diffusion coefficient is D ～ r ^?2, the intersection point corresponds to a penetration coefficient of about 0.37. The results obtained agree with the numerical data.     

A simple method for measuring plasma power in rf-GDOES instruments

A method for determining plasma power in rf-GDOES is presented. It is based on an effective resistance located in the inductive coil of the impedance matching. The amount of electrical power consumed in the matching system depends on the capacitive current flowing through the matching system, which depends on the applied voltage, the stray capacity, and the frequency. This correction method is experimentally evaluated and compared with the integral plasma power calculation.