Analysis of lignocellulosic feedstocks for biorefineries with a focus on the development of near infrared spectroscopy as a primary analytical tool.

The processing of lignocellulosic materials in modern biorefineries will allow for the production of transport fuels and platform chemicals that could replace petroleum-derived products. However, there is a critical lack of relevant detailed compositional information regarding feedstocks relevant to Ireland and Irish conditions. This research has involved the collection, preparation, and the analysis, with a high level of precision and accuracy, of a large number of biomass samples from the waste and agricultural sectors. Not all of the waste materials analysed are considered suitable for biorefining; for example the total sugar contents of spent mushroom composts are too low. However, the waste paper/cardboard that is currently exported from Ireland has a chemical composition that could result in high biorefinery yields and so could make a significant contribution to Ireland’s biofuel demands. Miscanthus was focussed on as a major agricultural feedstock. A large number of plants have been sampled over the course of the harvest window (October to April) from several sites. These have been separated into their anatomical fractions and analysed. This has allowed observations to be made regarding the compositional trends observed within plants, between plants, and between harvest dates. Projections are made regarding the extents to which potential chemical yields may vary. For the DIBANET hydrolysis process that is being developed at the University of Limerick, per hectare yields of levulinic acid from Miscanthus could be 20% greater when harvested early compared with a late harvest. The wet-chemical analysis of biomass is time-consuming. Near infrared spectroscopy (NIRS) has been developed as a rapid primary analytical tool with separate quantitative models developed for the important constituents of Miscanthus, peat, and (Australian) sugarcane bagasse. The work has demonstrated that accurate models are possible, not only for dry homogenous samples, but also for wet heterogeneous samples. For glucose (cellulose) the root mean square error of prediction (RMSEP) for wet samples is 1.24% and the R2 for the validation set (R²val) is 0.931. High accuracies are even possible for minor analytes; e.g. for the rhamnose content of wet Miscanthus samples the RMSEP is 0.03% and the R²val is 0.845. Accurate models have also been developed for pre-treated Miscanthus samples and are discussed. In addition, qualitative models have been developed. These allow for samples to be discriminated for on the basis of plant fraction, plant variety (giganteus/non-giganteus), harvest-period (early/late), and stand-age (one-year/older). Quantitative NIRS models have also been developed for peat, although the heterogeneity of this feedstock means that the accuracies tend to be lower than for Miscanthus. The development of models for sugarcane bagasse has been hindered, in some cases, by the limited chemical variability between the samples in the calibration set. Good models are possible for the glucose and total sugars content, but the accuracy of other models is poorer. NIRS spectra of Brazilian bagasse samples have been projected onto these models and onto those developed for Miscanthus, and the Miscanthus models appear to provide a better fit than the Australian bagasse models

Characterisation of Italian and Dutch forestry and agricultural residues for the applicability in the bio-based sector

Knowing the accurate composition of biomass is of crucial importance in order to assess and decide on the use and processes to be applied to specific biomass types. In this study, the composition of the lignocellulosic constituents present in forestry, agricultural and under utilised waste residues was assessed. Considering the increased interest on hemicellulose fractions for application in biomaterials and biomolecules, large emphasis has been given in detailing the monomeric constituents of the hemicellulose polymer. Lignin and cellulose, the two other major components of lignocellulosic biomass, were analysed and correlated with the trends in the other constituents. In the samples analysed, the total structural sugars content ranged from 26.0 to 67.5% of the biomass dry weight, indicating high variation between different feedstock and fractions. Hemicellulose concentration and composition also varied significantly (from 38.8% in birch (Betula Pendula Roth) foliage to 22.0 % in rice (Oryza sativa L.) straw) between the feedstock types and within the same feedstock type between different species and different fractions. The extractives content varied greatly between the different species (from 2.66 % to 30.47 % of the biomass dry weight) with high contents in certain fractions of feedstock suggesting more detailed compositional analysis of these extracts is warranted

Fates of Terrigenous Dissolved Organic Carbon in the Gulf of Maine

A significant amount of organic carbon is transported in dissolved form from soils to coastal oceans via inland water systems, bridging land and ocean carbon reservoirs. However, it has been discovered that the presence of terrigenous dissolved organic carbon (tDOC) in oceans is relatively limited. Therefore, understanding the fates of tDOC in coastal oceans is essential to account for carbon sequestration through land ecosystems and ensure accurate regional carbon budgeting. In this study, we developed a state-of-the-art modeling approach by coupling a land-to-ocean tDOC flux simulation model and a coastal tDOC tracking model to determine the potential fates of tDOC exported from three primary drainage basins in the Gulf of Maine (GoM). According to our findings, over half a year in the GoM, 56.4% of tDOC was mineralized. Biomineralization was responsible for 90% of that amount, with the remainder attributed to photomineralization. Additionally, 37% of the tDOC remained suspended in the GoM, and 6.6% was buried in the marine sediment

Silver Nanoscale Antisense Drug Delivery System for Photoactivated Gene Silencing

The unique photophysical properties of noble metal nanoparticles contribute to their potential as photoactivated drug delivery vectors. Here we demonstrate the synthesis and characterization of 60–80 nm silver nanoparticles (SNPs) decorated with thiol-terminated photolabile DNA oligonucleotides. <i>In vitro</i> assays and fluorescent confocal microscopy of treated cell cultures show efficient UV-wavelength photoactivation of surface-tethered caged ISIS2302 antisense oligonucleotides possessing internal photocleavable linkers. As a demonstration of the advantages of these novel nanocarriers, we investigate properties including: enhanced stability to nucleases, increased hybridization activity upon photorelease, and efficient cellular uptake as compared to commercial transfection vectors. Their potential as multicomponent delivery agents for oligonucleotide therapeutics is shown through regulation of ICAM-1 (Intracellular Adhesion Molecule-1) silencing. Our results suggest a means to achieve light-triggered, spatiotemporally controlled gene silencing <i>via</i> nontoxic silver nanocarriers, which hold promise as tailorable platforms for nanomedicine, gene expression studies, and genetic therapies

Appendix D. Detailed description of regional variations in simulated terrestrial DOC loading, water yield, river discharge, and deepening of the active layer.

Detailed description of regional variations in simulated terrestrial DOC loading, water yield, river discharge, and deepening of the active layer

Appendix B. Model calibration data for boreal needleleaf deciduous forests/wetlands.

Model calibration data for boreal needleleaf deciduous forests/wetlands

Electrospun Bio-Nanocomposite Scaffolds for Bone Tissue Engineering by Cellulose Nanocrystals Reinforcing Maleic Anhydride Grafted PLA

Electrospun fibrous bio-nanocomposite scaffolds reinforced with cellulose nanocrystals (CNCs) were fabricated by using maleic anhydride (MAH) grafted poly­(lactic acid) (PLA) as matrix with improved interfacial adhesion between the two components. Morphological, thermal, mechanical, and in vitro degradation properties as well as basic cytocompatibility using human adult adipose derived mesenchymal stem cells (hASCs) of MAH grafted PLA/CNC (i.e., MPLA/CNC) scaffolds were characterized. Morphological investigation indicated that the diameter and polydispersity of electrospun MPLA/CNC nanofibers were reduced with the increased CNC content. The addition of CNCs improved both the thermal stability and mechanical properties of MPLA/CNC composites. The MPLA/CNC scaffolds at the 5 wt % CNC loading level showed not only superior tensile strength (more than 10 MPa), but also improved stability during in vitro degradation compared with the MPLA and PLA/CNC counterparts. Moreover, the fibrous MPLA/CNC composite scaffolds were non-toxic to hASCs and capable of supporting cell proliferation. This study demonstrates that fibrous MPLA/CNC bio-nanocomposite scaffolds are biodegradable, cytocompatible, and possess useful mechanical properties for bone tissue engineering

Appendix A. Modifications of the Terrestrial Ecosystem Model to better represent decomposition and soil moisture dynamics in Arctic ecosystems.

Modifications of the Terrestrial Ecosystem Model to better represent decomposition and soil moisture dynamics in Arctic ecosystems

Appendix C. Detailed evaluation of simulated terrestrial DOC loading and river discharge.

Detailed evaluation of simulated terrestrial DOC loading and river discharge

Plasmon-Enhanced Photocleaving Dynamics in Colloidal MicroRNA-Functionalized Silver Nanoparticles Monitored with Second Harmonic Generation

The photocleaving dynamics of colloidal microRNA-functionalized nanoparticles are studied using time-dependent second harmonic generation (SHG) measurements. Model drug-delivery systems composed of oligonucleotides attached to either silver nanoparticles or polystyrene nanoparticles using a nitrobenzyl photocleavable linker are prepared and characterized. The photoactivated controlled release is observed to be most efficient on resonance at 365 nm irradiation, with pseudo-first-order rate constants that are linearly proportional to irradiation powers. Additionally, silver nanoparticles show a 6-fold plasmon enhancement in photocleaving efficiency over corresponding polystyrene nanoparticle rates, while our previous measurements on gold nanoparticles show a 2-fold plasmon enhancement compared to polystyrene nanoparticles. Characterizations including extinction spectroscopy, electrophoretic mobility, and fluorimetry measurements confirm the analysis from the SHG results. The real-time SHG measurements are shown to be a highly sensitive method for investigating plasmon-enhanced photocleaving dynamics in model drug delivery systems