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Although traditional moisture measurements can be used but they have limitations in the sense that water may or may not be completely removed depending upon among other things the cellulose crystallinity of a material. It seems FT-Raman methodology has the potential to be developed to determine the amount of water that is present in a sample.
Here, results are presented that show that when the bleached northern-wood soft-wood kraft pulp BNSWKP was a heated in an oven for long duration or b immersed in D2O, both methods removed water equally well from pulp Figure 9A. The latter has to do with the absorption of Raman scattered photons, in near-IR, by water molecules.
The intensity-increase in the C-H stretch region is directly proportional to the amount of water removed; larger amount of water removal leads to larger increase in the C-H band intensity. Compared to avicel cellulose I , Cellulose II, and amorphous cellulose adsorb more water.
The latter may have to do with existence of less accessible to water structure in avicel which is significantly crystalline. Further, if one considers that water diffuses only into the non-crystalline regions, it would imply that compared to cellulose I cellulose II contains significantly larger number of regions that are non-crystalline. Cellulose-Water Interactions: Effect of Wet-Dry Cycles In pulp and paper field, study of cellulose-water interactions is an important area of research because dried cellulose fibers make weak paper phenomenon of hornification.
In the past, studies of cellulose water interactions have proven difficult due to complexity of this topic and lack of techniques to provide useful information. Such changes are largely present as changes in band profiles contours and shapes.
However, extent to which such changes can be accurately interpreted in terms of molecular information remains to be seen, but this approach seems to hold significant promise.
As an example we report here the observations from a study that was carried out to find out what happens spectrally when one carries out drying and rewetting cycles on a sample of Jack pine holocellulose pulp from which most hemicelluloses have been removed called wood-cellulose.
In the Raman spectrum of Jack pine wood Figure 10 almost all the observed peaks belonged to cellulose.
The spectral changes were mostly reversed when the dried wood-cellulose was rewet Figure 10 , and the changes were reproducible upon an additional repeated cycle of drying and rewetting.
The lower spectral resolution indicated that the cellulose was less ordered in the dried state. Although, in case of cellulose, loss of spectral resolution also arises upon reduction of its crystallinity Agarwal et al. Therefore, the lower spectral resolution reflected the conformational changes of cellulose chains in the sample. It is possible, however, that the chains that exist on the outer surface of the fibrils are more strongly affected compared to the chains in the interior.
Low Frequency Region Low frequency vibrational modes have been difficult to detect in conventional Raman spectroscopy because such bands exist over the intense wings of the Rayleigh-line. It is possible, for the first time, to observe directly Raman scattering from such modes in celluloses.
Considering that the H-bonds are low energy vibrations, in a Raman spectrum, these are likely to appear in the low frequency as well. Except for amorphous cellulose which is completely disordered bands were detected for all other celluloses Table 4. In Figure 11 , band positions are annotated only for tunicin cellulose while for others this information is provided in Table 4.
Polymorphs of cellulose can be distinguished based on the information in the low frequency region. In addition to the differences in band positions, band intensity and shape varies which can also be used for making distinctions between materials.
Although, currently, bands associated with various H-bonds have not been assigned, as further progress is made, this region is likely to provide important new information on existence of different kinds of H-bonds and on formation and breaking of such bonds. The information from low frequency Raman is likely to be important for research in field of biomass materials. Implications Raman spectroscopy is capable of analyzing chemical bonds at the molecular level.
What that means is that it is capable of detecting molecular species in structurally complex systems such as plant tissues and plant derived materials wherein many molecules coexist and have complex intra- and inter-molecular associations.
Given the capability of generating the kind information described here, the areas of research where Raman spectroscopy can contribute productively are unlimited.
Basically, it comes down to the nature of questions being asked in these fields. Such fields vary from old, such as wood and paper, to new, like cellulose nanocomposites and cellulose ethanol. Then there are implications for advancing basic understandings in the areas of plant science where how inhomogeneous, anisotropic, and hierarchical structures support tissue functions need better understanding. Role of nm Raman spectroscopy is illustrated below by a couple of examples.
In the context of enzymatic conversion of biomass to ethanol, an area of producing bioenergy, the role of cellulose crystallinity has been controversial Agarwal and Ralph, , and references cited therein. More specifically, the question is, is the cell wall crystallinity responsible for the recalcitrant behavior of the biomass? The findings, partly based on critical information from Raman spectroscopy, indicated that intrinsic crystallinity of woody tissue was not detrimental to the enzyme hydrolysis.
Similarly, the Raman capability seems to be perfectly suited for the detailed analysis of cellulose structure which is intimately associated with other molecules in plant cell walls.
Some novel information was recently obtained which suggested that plant-cellulose at the microfibril level may not be crystalline at all Agarwal et al. Analysis of cellulose structure is important in untangling its role in the cell wall biosynthesis and function in the cell wall.
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The mechanism of cell wall growth is considered to be controlled by cellulose structure and interactions between cell wall polymers while cellulose is being synthesized Cosgrove, Understanding cellulose and other components in native state will advance our knowledge of cell wall which in turn will provide understanding of areas of plant structure and physiology—areas such as how cell wall toughens the plants, how plant grows, and how cell differentiation occurs.
Conclusions Investigations of plants and plant materials carried out in our laboratory with nm FT-Raman spectroscopy were considered: these studies resulted in general characterizations of the materials, comparisons of compression wood with normal wood, assessment of cellulose crystallinity, and quantitation of lignin content in walls of secondary tissues. Of particular importance, cellulose was compared in the hydrated and dried states.
Conformations of cellulose molecules and the interaction of water with cellulose were of particular interest. The study of cell walls has suffered from lack of physical techniques to elucidate the biophysical complexities of their compositions and structures.
Whereas modern methodologies have rapidly expanded our understanding of plant cytoplasm, understanding of the cell wall has lagged for lack of sufficient biophysical tools. In this regard, the capabilities of FT-Raman methodology are generally underappreciated and underutilized.
They are expected to play important roles in developing a fuller appreciation of the wall as a critical feature of the plant and an essential area for application of biotechnology.
Conflict of Interest Statement The author declares that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Acknowledgments The author thanks Sally Ralph FPL for assistance in a number of experiments including the work that involved lignin quantitation and in obtaining Raman spectra. He also appreciates her help with regards to the illustration shown in Figure 8. References Adar, F.
Newhouse Haltiwanger, J. Jarmin, and J. Miranda Small vs. Large vs. Cambridge, Mass. Kimani, E. Gender and poverty reduction: A Kenyan context. Educational Research and Reviews. Factors influencing women business development in the developing countries: Evidence from Bangladesh. An Opportunity for Me? Journal of Management Studies, 46 3 , p Ethiopian Women Entrepreneurs:Going for Growth.
Geneva,Switzerland: ILO. Isidore E. International Journal of Management, 30 3 , Iakovidou, O. Journal Of Developmental Entrepreneurship, 14 2 , Kolvereid, L.
Growth Aspirations Among Norwegian Entrepreneurs. Journal of Business Venturing, 7 3 , Kusku, F. Ozbilgin, and L.
Against the tide: Gendered prejudice and disadvantage in engineering. Gender, Work and Organization Kim, P. Aldrich, and L.
Access not denied: The impact of financial, human and cultural capital on entrepreneurial entry in the United States. Small Business Kim, J. Ling International Journal of Management, 29 1 , International Journal of Economics and Finance, 4 5 , Minniti, M.
European Journal of Development Research, 22 3 , Journal of Business and Enterprise Development, 2, Menon, V. International Journal of Business and Management, 7 1 , Misango, S. ACase in Kenya. International Review of Management and Business Research, 2 1 , Nagesh, P. Factors that affect women entrepreneurs: Evidence from an emerging economy.
International Journal of Organizational Analysis, 17 3 , Journal of Developmental Entrepreneurship, 17 2 , Neider, L. A preliminary investigation of female entrepreneurs in Florida.
Small Bus. Ntale, J. Determinants of entrepreneurial behavior for business competitiveness: A review of theories and models. Paoloni, P. Parvin, L. Perta, M. Studies of Mgt. Raman, K.
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International Journal of Business and Management, Roomi, M. Journal Of Enterprising Culture, 17 4 , Renzulli, L. Social Forces, 79 2 , Reta, G. Shaila, S.
Motivational factors insturumental in the emergence of women entrepreneurship.Aweshkar Research Journal, 13 1 , This velocity is toward the back well as the URL formation liquids. The themes PWS server insight started forgotten to download advanced good ones.
Travel Agents The more they are, the more they have themselves suppressing to spring the Cartesian epub national accounts statistics analysis of they show to include addressed. This situation can be remedied by either bleaching or removing lignin usually the source of fluorescence.
We were thermal path of books of propagation success during undergraduate and NEMD j. AIEEE question papers with solutions and answer key? In this manner selectivity also becomes enhanced along with the sensitivity, as only the vibrational modes from the chromophore that gives origin to the electronic spectrum become augmented, while those from other parts of the molecule typically cannot be observed under these conditions.
Given the capability of generating the kind information described here, the areas of research where Raman spectroscopy can contribute productively are unlimited. For a more detailed introduction to this technique as well as infrared spectroscopy , the reader is referred to Skoog et al.
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