<em>Cladophora glomerata</em> is a filamentous green alga that currently forms extensive blooms in nearshore areas of Lake Ontario, eastern Lake Erie, Lake Michigan, and isolated locations in Lake Huron. The biomass, areal coverage, algal bed characteristics, and tissue phosphorus concentrations of <em>Cladophora glomerata</em> were measured at 24 nearshore rocky sites along the northern shoreline of Lake Erie?s eastern basin between 1995-2002. Midsummer areal coverage at shallow depths (&le;5m) ranged from 4-100 %, with a median value of 96%. Peak seasonal biomass ranged from <1 to 940 g m^-2 dry mass (DM), with a median value of 171 g m^-2 DM. Tissue phosphorus varied seasonally, with initial high values in early May (0. 15 to 0. 27 % DM; median 0. 23 % DM) to midsummer seasonal low values during peak biomass (0. 03 to 0. 23 % DM; median 0. 06 % DM). A numerical <em>Cladophora</em> growth model (CGM) was revised and field-tested at 5 sites in eastern Lake Erie during 2002. The CGM is useful for: 1) Predicting <em>Cladophora</em> growth, biomass, and tissue phosphorus concentrations under non-point source P loading with no depth restrictions; 2) providing estimates of the timing and magnitude of the midsummer sloughing phenomenon; 3) determining the contribution of <em>Dreissena</em> invasion to the resurgence of <em>Cladophora</em> in eastern Lake Erie; and 4) developing management strategies for <em>Cladophora</em> abatement. The CGM was applied to investigate how the spatial and temporal patterns of <em>Cladophora</em> growth were influenced by the natural variability in environmental parameters in eastern Lake Erie. Seasonal patterns in <em>Cladophora</em> growth were strongly influenced by temperature, and peak depth-integrated biomass was strongly influenced by both available light and phosphorus. The photosynthetic capacity of field collected <em>Cladophora</em> was a poor predictor of the mid-summer sloughing phenomenon. The CGM, however, predicted that self-shading within the dense <em>Cladophora</em> mats would have caused negative growth rates at the base of the dense mats for 14 days prior to the sloughing event. The metabolic imbalances at the base of the <em>Cladophora</em> mats were driven primarily by the availability of light and were exacerbated by intermediate water temperatures (~23°C). The excellent agreement between model simulations and field data illustrates the ability of the CGM to predict tissue P and growth over a range of sites and depths in eastern Lake Erie and suggests potential for the model to be successfully applied in other systems.

<em>Cladophora</em> is a widespread freshwater filamentous cholorophyte genus and is frequently observed in eutrophic waters where it can produce large nuisance blooms. These blooms can have direct impacts on water intake for power generation, irrigation canals and can be aesthetically unpleasant. Much of the ecological and physiological studies on <em>Cladophora</em> have assumed that the populations of this genus in North America belong to the species <em>Cladophora glomerata</em>. However, this has never been tested despite that it is well documented that identifying freshwater <em>Cladophora</em> to the species level is difficult due morphological variability under different ecological conditions. In addition, the species epithets for freshwater <em>Cladophora</em> are based on European collections and it is not clear if these should be applied to North America. This study examines approximately 40 collections of <em>Cladophora</em> from the Laurentian Great Lakes and 43 from various locations in North America ranging from the Northwest Territories to Puerto Rico. Initially we determined the nucleotide sequences of the internal transcribed spacer (ITS) region of the nuclear ribosomal cistron and observed sequence divergence to be low (0-3%), demonstrating an inability for this marker to resolve species delineation as divergence of this region was low. Amplification of the inter-simple sequence repeat (ISSR) regions were used to analyze microsatellite motif frequency throughout the genome to evaluate the biogeography relationships, including diversity, of freshwater <em>Cladophora</em> sp. five different primers were used on 70 individuals. UPGMA analyses of the presence/absence of bands demonstrate that each of the Great Lake populations separate into groups according to the Lake they were initially sampled from. However, collections from North America are highly variable and do not form well supported biogeographic clades. In addition, these collections appear to be distinct from type cultures of freshwater <em>Cladophora</em> from Europe. Supplementary morphological analysis using suggested taxonomically valid criterion (length and diameter of main axis, ultimate branch, and apical cell) none were able to differentiate Great Lake populations.

Nanocellulose has received considerable interest during the last decade because it is renewable and biodegradable, and has excellent mechanical properties, nanoscale dimensions and wide functionalization possibilities. It is considered to be a unique and versatile platform on which new functional materials can be based. This thesis focuses on nanocellulose from wood (NFC) and from Cladophora algae (CNC), functionalized with surface charges or coated with the conducting polymer polypyrrole (PPy), aiming to study the influence of synthesis processes on structural and electrochemical properties of such materials and assess their biocompatibility. The most important results of the work demonstrated that 1) CNC was oxidized to the same extent using electrochemical TEMPO-mediated oxidation as with conventional TEMPO processes, which may facilitate easier reuse of the reaction medium; 2) NFC and CNC films with or without surface charges were non-cytotoxic as assessed by indirect in vitro testing. Anionic TEMPO-CNC films promoted fibroblast adhesion and proliferation in direct in vitro cytocompatibility testing, possibly due to its aligned fibril structure; 3) Rinsing of PPy-coated nanocellulose fibrils, which after drying into free-standing porous composites are applicable for energy storage and electrochemically controlled ion extraction, significantly degraded the PPy coating, unless acidic rinsing was employed. Only minor degradation was observed during long-term ambient storage; 4) Variations in the drying method as well as type and amount of nanocellulose offered ways of tailoring the porosities of nanocellulose/PPy composites between 30% and 98%, with increments of ~10%. Supercritical CO2-drying generated composites with the largest specific surface area yet reported for nanocellulose/conducting polymer composites (246 m2/g). The electrochemical oxidation rate was found to be controlled by the composite porosity; 5) In blood compatibility assessments for potential hemodialysis applications, heparinization of CNC/PPy composites was required to obtain thrombogenic properties comparable to commercial hemodialysis membranes. The pro-inflammatory characteristics of non-heparinized and heparinized composites were, to some extent, superior to commercial membranes. The heparin coating did not affect the solute extraction capacity of the composite. The presented results are deemed to be useful for tuning the properties of systems based on the studied materials in e.g. energy storage, ion exchange and biomaterial applications.

Surface streams in karst landscapes are often characterized by high nutrient levels due to incomplete filtration through series of innumerable, below-ground conduits. Seasonal growth of the filamentous alga, Cladophora, is typically associated with nutrient-rich waters. This research compared macroinvertebrate food web structure between riverine reaches with contrasting underlying karst topography, nutrient levels, and Cladophora cover during summer 2012 and autumn 2013. Recent work in these reaches found a high correlation between Cladophora cover and nutrient content, particularly nitrate. Four questions were addressed during this study: 1. Do longitudinal trends in algal and consumer δ13C values relate to decreased DIC availability in larger watersheds? 2. Are trophic niche breadths narrower in more karstified reaches than in less karstified reaches due to longitudinal differences in Cladophora standing stocks? 3. Do differences in trophic-dynamic relationships between primary consumers and their food resources reflect the marked distinction in Cladophora standing stocks in two sections of the upper Green River that flow through differing levels of karstification? 4. Are consumers assimilating primarily autochthonous or allochthonous food resources? Consumers and algae became more 13C-depleted in downstream reaches, which is opposite to published data in other streams. Underlying causes for this pattern are uncertain, but one plausible cause is an increase in DIC availability downstream. Karstrelated hydrology may potentially alter or even reverse normal longitudinal gradients within in-stream producer and subsequently, consumer δ13C values. Since consumers were sampled during low-Cladophora conditions during 2013 and within a few weeks of the onset of the Cladophora bloom in 2012, stable isotopic results may be more representative of primary consumer diets during pre- Cladophora bloom periods. Although Cladophora cover was significantly higher in downstream reaches during both years, food-web structure was similar in all reaches. Consumer niche breadth was similar across reaches, and mixing model analyses suggested that primary consumers in all reaches assimilated similar amounts of Cladophora. The contribution of both autochthonous and allochthonous food resources to the assimilated diet of primary consumers appeared to be similarly important. These results suggest that allochthonous resources may be important in some midreach food webs, especially during periods of low algal growth.

In the past decade there has been increasing interest in exploring the use of nanocellulose in medicine. However, the influence of the physicochemical properties of nanocellulose on the material´s biocompatibility has not been fully investigated.  In this thesis, thin films of nanocellulose from wood (NFC) and from Cladophora algae (CC) were modified by the addition of charged groups on their surfaces and the influence of these modifications on the material´s physicochemical properties and on cell responses in vitro was studied. The results indicate that the introduction of charged groups on the surface of NFC and CC results in films with decreased surface area, smaller average pore size and a more compact structure compared with the films of unmodified nanocelluloses. Furthermore, the fibres in the carboxyl-modified CC films were uniquely aggregated and aligned, a state which tended to become more prevalent with increased surface-group density. The biocompatibility studies showed that NFC films containing hydroxypropyltrime-thylammonium (HPTMA) groups presented a more cytocompatible surface than unmodified NFC and carboxymethylated NFC regarding human dermal fibroblasts. Carboxymethyl groups resulted in NFC films that promoted inflammation, while HPTMA groups had a passivating effect in terms of inflammatory response.  On the other hand, both modified CC films behaved as inert materials in terms of the inflammatory response of monocytes/macrophages and, under pro-inflammatory stimuli, they suppressed secretion of the pro-inflammatory cytokine TNF-α, with the effects of the carboxylated CC film more pronounced than those of the HPTMA CC material.  Carboxyl CC films showed good cytocompatibility with fibroblasts and osteoblastic cells. However, it was necessary to reach a threshold value in carboxyl-group density to obtain CC films with cytocompatibility comparable to that of commercial tissue culture material.  The studies presented here highlight the ability of the nanocellulose films to modulate cell behaviour and provide a foundation for the design of nanocellulose-based materials that trigger specific cell responses. The bioactivity of nanocellulose may be optimized by careful tuning of the surface properties. The outcomes of this thesis are foreseen to contribute to our fundamental understanding of the biointerface phenomena between cells and nanocellulose as well as to enable engineering of bioinert, bioactive, and bioadaptive materials.

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<p>Cellulose powders from various sources were manufactured and characterized to investigate the influence of their crystallinity index, surface area, and pore volume on sorption phenomena and the relevant pharmaceutical functionality. The influence of the cellulose crystallinity index on moisture sorption was important at low and intermediate relative humidities. At high relative humidities, properties such as surface area and pore volume took precedence in governing the moisture sorption process.</p><p>The theory of physical adsorption of gases onto fractal surfaces was useful for understanding the distribution of water in cellulose and the inner nanoscale structure of cellulose particles. It was found that, as a consequence of swelling, moisture induces a fractal nanopore network in cellulose powders that have a low or intermediate degree of crystallinity. On the other hand, no swelling occurs in highly crystalline cellulose powders and moisture sorption is restricted to the walls of the open pores.</p><p>No correlation was found between the cellulose crystallinity index and the incorporation and release of nicotine in cellulose mixtures. By loading nicotine in highly porous matrices of the Cladophora sp. algae cellulose, higher stability against oxidative degradation, higher loading capacity, and more steady release into an air-stream was achieved than when commercially available microcrystalline cellulose was loaded.</p><p>It was also shown that, by manipulating the structure of cellulose, the undesired hydrolysis of acetylsalicylic acid in mixtures with cellulose can be avoided. It was suggested that a broad hysteresis loop between the moisture adsorption and desorption curves of isotherms at low relative humidities could be indicative of an improved compatibility between acetylsalicylic acid and cellulose.</p><p>In all, this thesis demonstrates how the pharmaceutical functionality of microcrystalline cellulose can be improved via engineering of the structure of native cellulose powders.</p>

Cellulose powders from various sources were manufactured and characterized to investigate the influence of their crystallinity index, surface area, and pore volume on sorption phenomena and the relevant pharmaceutical functionality. The influence of the cellulose crystallinity index on moisture sorption was important at low and intermediate relative humidities. At high relative humidities, properties such as surface area and pore volume took precedence in governing the moisture sorption process. The theory of physical adsorption of gases onto fractal surfaces was useful for understanding the distribution of water in cellulose and the inner nanoscale structure of cellulose particles. It was found that, as a consequence of swelling, moisture induces a fractal nanopore network in cellulose powders that have a low or intermediate degree of crystallinity. On the other hand, no swelling occurs in highly crystalline cellulose powders and moisture sorption is restricted to the walls of the open pores. No correlation was found between the cellulose crystallinity index and the incorporation and release of nicotine in cellulose mixtures. By loading nicotine in highly porous matrices of the Cladophora sp. algae cellulose, higher stability against oxidative degradation, higher loading capacity, and more steady release into an air-stream was achieved than when commercially available microcrystalline cellulose was loaded. It was also shown that, by manipulating the structure of cellulose, the undesired hydrolysis of acetylsalicylic acid in mixtures with cellulose can be avoided. It was suggested that a broad hysteresis loop between the moisture adsorption and desorption curves of isotherms at low relative humidities could be indicative of an improved compatibility between acetylsalicylic acid and cellulose. In all, this thesis demonstrates how the pharmaceutical functionality of microcrystalline cellulose can be improved via engineering of the structure of native cellulose powders.

Conductive paper materials consisting of conductive polymers and cellulose are promising for high-tech applications (energy storage and biosciences) due to outstanding aspects of environmental friendliness, mechanical flexibility, electrical conductivity and efficient electroactive behavior. Recently, a conductive composite paper material was developed by covering the individual nanofibers of cellulose from the green algae Cladophora with a polypyrrole (PPy) layer. The PPy-Cladophora cellulose composite paper is featured with high surface area (80 m2 g-1), electronic conductivity (~2 S cm-1), thin conductive layer (~50 nm) and easily up-scalable manufacturing process. This doctoral thesis reports the development of the PPy-Cladophora composite as an electrode material in electrochemically controlled solid phase ion-exchange of biomolecules and all-polymer based energy storage devices. First, electrochemical ion-exchange properties of the PPy-Cladophora cellulose composite were investigated in electrolytes containing three different types of anions, and it was found that smaller anions (nitrate and chloride) are more readily extracted by the composite than lager anions (p-toluene sulfonate). The influence of differently sized oxidants used during polymerization on the anion extraction capacity of the composite was also studied. The composites synthesized with two different oxidizing agents, i.e. iron (III) chloride and phosphomolybdic acid (PMo), were investigated for their ability to extract anions of different sizes. It was established that the number of absorbed ions was larger for the iron (III) chloride-synthesized sample than for the PMo-synthesized sample for all four electrolytes studied. Further, PPy-Cladophora cellulose composites have shown remarkable electrochemically controlled ion extraction capacities when investigated as a solid phase extraction material for batch-wise extraction and release of DNA oligomers. In addition, composite paper was also investigated as an electrode material in the symmetric non-metal based energy storage devices. The salt and paper based energy storage devices exhibited charge capacities (38−50 mAh g−1) with reasonable cycling stability, thereby opening new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems. Finally, micron-sized chopped carbon fibers (CCFs) were incorporated as additives to improve the charge-discharge rates of paper-based energy storage devices and to enhance the DNA release efficiency. The results showed the independent cell capacitances of ~60-70 F g-1 (upto current densities of 99 mA cm2) and also improved the efficiency of DNA release from 25 to 45%.