The variations and climatic significance of D/H ratios in the carbon-bound hydrogen of cellulose in trees

The σD values of nitrated cellulose from a variety of trees covering a wide geographic range have been measured. These measurements have been used to ascertain which factors are likely to cause σD variations in cellulose C-H hydrogen.

It is found that a primary source of tree σD variation is the σD variation of the environmental precipitation. Superimposed on this are isotopic variations caused by the transpiration of the leaf water incorporated by the tree. The magnitude of this transpiration effect appears to be related to relative humidity.

Within a single tree, it is found that the hydrogen isotope variations which occur for a ring sequence in one radial direction may not be exactly the same as those which occur in a different direction. Such heterogeneities appear most likely to occur in trees with asymmetric ring patterns that contain reaction wood. In the absence of reaction wood such heterogeneities do not seem to occur. Thus, hydrogen isotope analyses of tree ring sequences should be performed on trees which do not contain reaction wood.

Comparisons of tree σD variations with variations in local climate are performed on two levels: spatial and temporal. It is found that the σD values of 20 North American trees from a wide geographic range are reasonably well-correlated with the corresponding average annual temperature. The correlation is similar to that observed for a comparison of the σD values of annual precipitation of 11 North American sites with annual temperature. However, it appears that this correlation is significantly disrupted by trees which grew on poorly drained sites such as those in stagnant marshes. Therefore, site selection may be important in choosing trees for climatic interpretation of σD values, although proper sites do not seem to be uncommon.

The measurement of σD values in 5-year samples from the tree ring sequences of 13 trees from 11 North American sites reveals a variety of relationships with local climate. As it was for the spatial σD vs climate comparison, site selection is also apparently important for temporal tree σD vs climate comparisons. Again, it seems that poorly-drained sites are to be avoided. For nine trees from different "well-behaved" sites, it was found that the local climatic variable best related to the σD variations was not the same for all sites.

Two of these trees showed a strong negative correlation with the amount of local summer precipitation. Consideration of factors likely to influence the isotopic composition of summer rain suggests that rainfall intensity may be important. The higher the intensity, the lower the σD value. Such an effect might explain the negative correlation of σD vs summer precipitation amount for these two trees. A third tree also exhibited a strong correlation with summer climate, but in this instance it was a positive correlation of σD with summer temperature.

The remaining six trees exhibited the best correlation between σD values and local annual climate. However, in none of these six cases was it annual temperature that was the most important variable. In fact annual temperature commonly showed no relationship at all with tree σD values. Instead, it was found that a simple mass balance model incorporating two basic assumptions yielded parameters which produced the best relationships with tree σD values. First, it was assumed that the σD values of these six trees reflected the σD values of annual precipitation incorporated by these trees. Second, it was assumed that the σD value of the annual precipitation was a weighted average of two seasonal isotopic components: summer and winter. Mass balance equations derived from these assumptions yielded combinations of variables that commonly showed a relationship with tree σD values where none had previously been discerned.

It was found for these "well-behaved" trees that not all sample intervals in a σD vs local climate plot fell along a well-defined trend. These departures from the local σD VS climate norm were defined as "anomalous". Some of these anomalous intervals were common to trees from different locales. When such widespread commonalty of an anomalous interval occurred, it was observed that the interval corresponded to an interval in which drought had existed in the North American Great Plains.

Consequently, there appears to be a combination of both local and large scale climatic information in the σD variations of tree cellulose C-H hydrogen.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.

Biodeterioration of cellulose materials in Karingote, Nileswaram, Kavvayi and Ramapuram Backwater systems of Kerala

The hydrographic conditions prevailing in an estuarine system along the southwest coast of India are described. The nature of destruction of timber in these backwaters has been examined in detail which revealed the existence of 8 species of shipworms, 2 species each of pholads and isopods. The shipworms are represented by Dicyathifer manni, Lyrodus pedicellatus, Teredo furcifera, T. clappi, Nausitora dunlopei, Bankia carinata, B. campanellata; the pholads by Martesia striata and M. (Purticoma) nairi; and the isopods by Sphaeroma terebrans and S. annandalei. The incidence and relative abundance of these pests are discussed in relation to the salinity profile of the estuary.

Kinetic Model Study on Enzymatic Hydrolysis of Cellulose Using Artificial Neural Networks

Enzymatic hydrolysis of cellulose was highly complex because of the unclear enzymatic mechanism and many factors that affect the heterogeneous system. Therefore, it is difficult to build a theoretical model to study cellulose hydrolysis by cellulase. Artificial neural network (ANN) was used to simulate and predict this enzymatic reaction and compared with the response surface model (RSM). The independent variables were cellulase amount X-1, substrate concentration X-2, and reaction time X-3, and the response variables were reducing sugar concentration Y-1 and transformation rate of the raw material Y-2. The experimental results showed that ANN was much more suitable for studying the kinetics of the enzymatic hydrolysis than RSM. During the simulation process, relative errors produced by the ANN model were apparently smaller than that by RSM except one and the central experimental points. During the prediction process, values produced by the ANN model were much closer to the experimental values than that produced by RSM. These showed that ANN is a persuasive tool that can be used for studying the kinetics of cellulose hydrolysis catalyzed by cellulase.

Cellulose acetate polymer film modified microstructured polymer optical fiber towards a nitrite optical probe

A novel microstructured polymer optical fiber (MPOF) probe for nitrites (NO(2)(-)) detection was made by forming rhodamine 6G (Rh 6G)-doped cellulose acetate (CA) on the side wall of array holes in a MPOF It was found that the MPOF probe only have a response to nitrites in a certain concentration of sulfuric acid solution The calibration graph of fluorescence intensity versus nitrites concentration was linear in the range of 2.0 x 10(-4) g/ml-5.0 x 10(-3) g/ml. The method possesses case of chemical modification, low cost design, and potential for direct integration with existing instrumentation, and has been applied to the determination of nitrites in real samples with satisfactory results. (C) 2010 Elsevier B.V. All rights reserved

Preparation and performance of cellulose acetate/polyethyleneimine blend microfiltration membranes and their applications

A modified microfiltration membrane has been prepared by blending a matrix polymer with a functional polymer. Cellulose acetate (CA) was blended with polyethyleneimine (PEI), which was then crosslinked by polyisocyanate, in a mixture of solvents. In the membrane, PEI can supply coupling sites for ligands in affinity separation or be used as ligands for metal chelating, removal of endotoxin or ion exchange. The effects of the time of phase inversion induced by water vapor, blended amount of PEI and amount of crosslinking agent on membrane performance were investigated. The prepared blend membranes have specific surface area of 12.04-24.11 m(2)/g and pure water flux (PWF) of 10-50 ml/cm(2) min with porosity of 63-75%. The membranes, made of 0.15 50 wt.% PEI/CA ratio and 0.5 crosslinking agent/PEI ratio, were applied to adsorbing Cu2+ and bovine serum albumin (BSA) individually. The maximum adsorption capacity of Cu2+ ion on the blend membrane is 7.42 mg/g dry membrane. The maximum adsorption capacities of BSA on the membranes with and without chelating Cu2+ ion are 86.6 and 43.8 mg/g dry membrane, respectively. (C) 2004 Elsevier B.V. All rights reserved.

Influence of drying method on morphology and properties of asymmetric cellulose hollow fiber membrane

Using a dry/wet spinning process, asymmetric cellulose hollow fiber membranes (CHFM) were prepared from a dope composed of cellulose/N-methylmorpholine-N-oxide/water. The formation mechanism for the finger-like macrovoids at the inner portion of as-spun fibers was explained. Naturally drying and three solvent exchange drying methods were tried to investigate their influence on morphology and properties of CHFM. It was found that the ethanol-hexane exchange drying was an appropriate method to minimize morphology change of the as-spun CHFM, whereas the naturally drying caused the greatest shrinkage of the fibers that made the porous membrane become dense. The result, CHFM from ethanol-hexane exchange drying performed the highest gas permeation rate but gas permeation of the naturally dried membrane could not be detectable. The resultant CHFM from the ethanol-hexane exchange drying also showed acceptable, mechanical properties, thus it was proposed to be an appropriate method for gas separation purpose. The experimental results supported the proposed drying mechanism of CHFM. The free water would evaporate or be replaced by a solvent that subsequently would evaporate but the bonded water would remain in the membrane. What dominated the changes of membrane morphology during drying should be. the molecular affinities of cellulose-water, water-solvent and solvent-solvent. (C) 2004 Elsevier B.V. All rights reserved.

Gas permeation performance of cellulose hollow fiber membranes made from the cellulose/N-methylmorpholine-N-oxide/H2O system

Cellulose hollow fiber membranes (CHFM) were prepared using a spinning solution containing N-methylmorpholine-N-oxide as solvent and water as a nonsolvent additive. Water was also used as both the internal and external coagulant. It was demonstrated that the phase separation mechanism of this system was delayed demixing. The CHFM was revealed to be homogeneously dense structure after desiccation. The gas permeation properties of CO2, N-2, CH4, and H-2 through CHFM were investigated as a function of membrane water content and operation pressure. The water content of CHFM had crucial influence on gas permeation performance, and the permeation rates of all gases increased sharply with the increase of membrane water content. The permeation rate of CO2 increased with the increase of operation pressure, which has no significant effect on N-2, H-2, and CH4. At the end of this article a detailed comparison of gas permeation performance and mechanism between the CHFM and cellulose acetate flat membrane was given. (C) 2003 Wiley Periodicals, Inc.

Synthesis of chiral stationary phases with radical polymerization reaction of cellulose phenylcarbamate derivatives and vinylized silica gel

Cellulose phenylcarbamate derivatives having methacrylate groups were synthesized with regioselective and non-regioselective procedures. These derivatives were chemically immobilized onto a vinylized silica gel, respectively, via a radical co-polymerization reaction. The immobilization was efficiently attained using a small amount of AIBN. The chiral recognition abilities of the prepared chiral stationary phases (CSPs) were evaluated by HPLC resolution of test enantiomers. It was observed that most of the enantiomers were completely resolved with markedly high column efficiency of 30,000-40,000 plates per metre for the eluted peaks. The effect of the amount of methacrylolyl chloride used for preparation on resolution was investigated. A direct comparison of the chiral recognition ability was made on the regioselectively and non-regioselectively prepared CSPs. In addition, the chemically bonded-type of CSPs were found to be relatively stable with addition of solvents such as tetrahydrofuran (THF) and chloroform into the mobile phase, which can lead to the dissolution of cellulose derivatives on the coated CSPs. Thus the choice of solvents used as the mobile phase is greatly extended and better resolution of several test enantiomers was observed on the prepared CSPs with THF and chloroform as a composition in the mobile phase. The batch-to-batch and run-to-run reproducibility was also discussed on the newly prepared CSPs. (C) 2004 Elsevier B.V. All rights reserved.

Separation of enantiomers by nanoliquid chromatography and capillary electrochromatography using a bonded cellulose trisphenylcarbamate stationary phase

A cellulose trisphenylcarbamate-bonded chiral stationary phase was applied to nano-liquid chromatography (nano-LC) and capillary electrochromatography (CEC) with nonaqueous and aqueous solutions as the mobile phases. Several chiral compounds were successfully resolved on the prepared phase by nano-LC. The applicability of nonaqueous CEC on a cellulose derivative stationary phase was investigated with the organic solvents methanol, hexane, 2-propanol, and tetrahydrofuran (THF) containing acetic acid, as well as triethylamine as the mobile phases. Enantiomers of warfarin and praziquantel were baseline-resolved with plate numbers of 82 300 and 38 800 plates/m, respectively, for the first eluting enantiomer. The influence of applied voltage, concentration of nonpolar solvent, apparent pH, and buffer concentration in the mobile phase on the electroosmotic flow (EOF) and the mobility of the enantiomers was evaluated. Enantioseparations of traps-stilbene oxide and praziquantel were also achieved in aqueous CEC with plate numbers of 111 100 and 107 400 plates/m, respectively, for the first eluting enantiomer. A comparison between nonaqueous CEC and aqueous CEC based on a cellulose trisphenylcarbamate stationary phase was discussed. Pressure-assisted CEC was examined for the chiral separation of praziquantel and faster analysis with high enantioselectivity was acquired with the proper pressurization of the inlet vial.