Feedstock/pretreatment screening for bioconversion of sugar and lignin streams via deacetylated disc-refining.

Recent publications have shown the benefits of deacetylation disc-refining (DDR) as a pretreatment process to deconstruct biomass into sugars and lignin residues. Major advantages of DDR pretreatment over steam and dilute acid pretreatment are the removal of acetyl and lignin during deacetylation. DDR does not generate hydroxymethylfurfural (HMF) and furfural which are commonly produced from steam and dilute acid pretreatments. Acetate, lignin, HMF, and furfural are known inhibitors during enzymatic hydrolysis and fermentation. Another advantage of deacetylation is the production of lignin-rich black liquor, which can be upgraded to other bioproducts. Furthermore, due to the lack of sugar degradation during deacetylation, DDR has significantly less sugar loss than other pretreatment methods. Previous studies for DDR have primarily focused on corn stover, but lacked the investigative studies of other feedstocks. This study was designed to screen various DDR process conditions at pilot scale using three different feedstocks, including corn stover, poplar, and switchgrass. The impact of the pretreatment conditions was evaluated by testing hydrolysates for bioconversion to 2,3-butanediol. Pretreatment of biomass by DDR showed high-conversion-yields and 2,3-BDO fermentation production yields. Techno-economic analysis (TEA) of the pretreatment for biomass to sugar was also developed based on NREL's Aspen Model. This study shows that the cellulose and hemicellulose in poplar was more recalcitrant than herbaceous feedstocks which ultimately drove up the sugar cost. Switchgrass was also more recalcitrant than corn stover but less than poplar.

Characterization data of palladium-alumina on activated biochar catalyst for hydrogenolysis reactions.

This article presents experimental data on the techniques used for the characterization of Pd-Al2O3 supported on activated biochar (2Pd-5Al/ABC) catalyst. The reported data is collected as a part of the research on the 2Pd-5Al/ABC catalyst used for lignin hydrogenolysis [1]. The data on X-ray powder diffraction, ammonia-temperature programmed desorption, pyridine diffuse reflectance infrared Fourier transform spectroscopy, and high-resolution scanning electron microscopy of various catalysts are valuable to study the changes in surface morphology and acidity upon metal loading. The data from thermogravimetric analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy-energy dispersive X-ray spectroscopy are also provided to understand the thermal stability, ionic state of various metals and elemental composition of the catalyst, respectively. The data provided can be used for developing novel catalysts from renewable biochar, and the characterization of noble metal-metal oxide loaded catalysts can aid researchers to design composite catalytic materials for various applications.

Development of a carbon clad core-shell silica for high speed two-dimensional liquid chromatography.

We recently introduced a new method to deposit carbon on fully porous silicas (5 µm) to address some of the shortcomings of carbon clad zirconia (C/ZrO(2)), which has rather low retention due to its low surface area (20-30 m(2)/g). The method enables the introduction of a thin, homogeneous layer of Al(III) on silica to serve as catalytic sites for carbon deposition without damaging the silica's native pore structure. Subsequent carbon deposition by chemical vapor deposition resulted in chromatographically useful carbon phases as shown by good efficiencies and higher retentivity relative to C/ZrO(2). Herein, we use the above method to develop a novel carbon phase on superficially porous silica (2.7 µm). This small, new form of silica offers better mass transfer properties and higher efficiency with lower column back pressures as compared to sub 2 µm silica packings, which should make it attractive for use as the second dimension in fast two-dimensional LC (LC × LC). After carbon deposition, several studies were conducted to compare the new packing with C/ZrO(2). Consistent with work on 5 µm fully porous silica, the metal cladding did not cause pore blockage. Subsequent carbon deposition maintained the good mass transfer properties as shown by the effect of velocity on HETP. The new packing exhibits efficiencies up to ∼5.6-fold higher than C/ZrO(2) for polar compounds. We observed similar chromatographic selectivity for all carbon phases tested. Consequently, the use of the new packing as the second dimension in fast LC×LC improved the peak capacity of fast LC × LC. The new material gave loading capacities similar to C/ZrO(2), which is rather as expected based on the surface areas of the two phases.

New method for development of carbon clad silica phases for liquid chromatography: Part I. Preparation of carbon phases.

Owing to its combination of unique selectivity and mechanical strength, commercial carbon clad zirconia (C/ZrO2) has been widely used for many applications, including fast two-dimensional liquid chromatography (2DLC). However, the low surface area available (only 20-30 m²/g for commercial porous ZrO2) limits its retentivity. We have recently addressed this limitation by developing a carbon phase coated on the high surface area of HPLC grade alumina (C/Al2O3). This material provides higher retentivity and comparable selectivity, but its use is still limited by how few HPLC quality types of alumina particles (e.g., particle size, surface area, and pore size) are available. In this work, we have developed useful carbon phases on silica particles, which are available in various particle sizes, pore sizes and forms of HPLC grade. To make the carbon phase on silica, we first treat the silica surface with a monolayer or less of metal cations that bind to deprotonated silanols to provide catalytic sites for carbon deposition. After Al (III) treatment, a carbon phase is formed on the silica surface by chemical vapor deposition at 700 °C using hexane as the carbon source. The amount of Al (III) on the surface was varied to assess its effect on carbon deposition, and the carbon loading was varied at different Al (III) levels to assess its effect on the chromatographic properties of the various carbon adsorbents. We observed that use of a concentration of Al (III) corresponding to a full monolayer leads to the most uniform carbon coating. A carbon coating sufficient to cover all the Al (III) sites, required about 4-5 monolayers in this work, provided the best chromatographic performance. The resulting carbon phases behave as reversed phases with reasonable efficiency (50,000-79,000 plates/m) for non-aromatic test species.

Preparation and evaluation of carbon coated alumina as a high surface area packing material for high performance liquid chromatography.

The retention of polar compounds, the separation of structural isomers and thermal stability make carbonaceous materials very attractive stationary phases for liquid chromatography (LC). Carbon clad zirconia (C/ZrO(2)), one of the most interesting, exhibits unparalleled chemical and thermal stability, but its characteristically low surface area (20-30 m(2)/g) limits broader application as a second dimension separation in two-dimensional liquid chromatography (2DLC) where high retentivity and therefore high stationary phase surface area are required. In this work, we used a high surface area commercial HPLC alumina (153 m(2)/g) as a support material to develop a carbon phase by chemical vapor deposition (CVD) at elevated temperature using hexane vapor as the carbon source. The loading of carbon was varied by changing the CVD time and temperature, and the carbon coated alumina (C/Al(2)O(3)) was characterized both physically and chromatographically. The resulting carbon phases behaved as a reversed phase similar to C/ZrO(2). At all carbon loadings, C/Al(2)O(3) closely matched the unique chromatographic selectivity of carbon phases, and as expected the retentivity was increased over C/ZrO(2). Excess carbon - the amount equivalent to 5 monolayers--was required to fully cover the oxide support in C/Al(2)O(3), but this was less excess than needed with C/ZrO(2). Plate counts were 60,000-76,000/m for 5 µm particles. Spectroscopic studies (XPS and FT-IR) were also conducted; they showed that the two materials were chemically very similar.

Application of silica-based hyper-crosslinked sulfonate-modified reversed stationary phases for separating highly hydrophilic basic compounds.

The separation and determination of hydrophilic basic compounds are of great importance in many fields including clinical and biological research, pharmaceutical development and forensic analysis. However, the most widely used analytical separation technique in these disciplines, reversed-phase liquid chromatography (RPLC), usually does not provide sufficient retention for several important classes of highly hydrophilic basic compounds including catecholamines, many drug metabolites and many drugs of abuse. Commonly eluents having little or no organic modifier and/or strong ion pairing agents must be used to achieve sufficient retention and separation. Use of highly aqueous eluents can lead to column failure by dewetting, resulting in poor retention, low selectivity and irreproducibility and slow recovery of performance. The use of a strong ion pairing agent to increase retention renders the separation incompatible with mass spectrometric detection and complicates preparative separations. This paper describes the successful applications of a novel type of silica-based, hyper-crosslinked, sulfonate-modified reversed stationary phase, denoted as (-)SO(3)-HC-C(8)-L, for the separation of highly hydrophilic cations and related compounds by a hydrophobically assisted cation-exchange mechanism. Compared to conventional reversed-phases, the (-)SO(3)-HC-C(8)-L phase showed significantly improved retention and separation selectivity for hydrophilic amines. Concurrently, due to the presence of both cation-exchange and reversed-phase retention mechanisms and the high acid stability of hyper-crosslinked phases, the separation can be optimized by changing the type or concentration of ionic additive or organic modifier, and by varying the column temperature. In addition, gradients generated by programming the concentration of either the ionic additive or the organic modifier can be applied to reduce the analysis time without compromising resolution. Furthermore, remarkably different chromatographic selectivities, especially toward cationic solutes, were observed upon comparing the (-)SO(3)-HC-C(8)-L phase with conventional reversed-phases. We believe that the combination of these two types of stationary phases will be very useful in two-dimensional liquid chromatography.

Fast gradient elution reversed-phase high-performance liquid chromatography with diode-array detection as a high-throughput screening method for drugs of abuse. I. Chromatographic conditions.

A new approach for the high-throughput screening of biological samples to detect the presence of regulated intoxicants has been developed by modifying a conventional gradient elution high-performance liquid chromatograph (HPLC). The goal of this work was to improve the speed of gradient elution screening methods over current approaches by optimizing the operational parameters of both the column and the instrument without compromising the reproducibility of the retention times, which is the basis for the identification of intoxicant compounds. Most importantly, the novel instrument configuration substantially reduces the time needed to re-equilibrate the column between consecutive gradient runs, thereby reducing the total time for each analysis. The total analysis time for each gradient elution run is only 2.80 min, including 0.30 min for column re-equilibration between analyses. Retention times of standard calibration solutes are reproducible to better than 0.002 min in consecutive runs. A corrected retention index was adopted to account for day-to-day and column-to-column variations in retention time. For a set of forty-seven target compounds, the discriminating power and mean list length were found to be 0.95 and 3.26, respectively. In comparison to previous work with similar numbers of target compounds, the current approach provides an order of magnitude improvement in analysis time, and a four-fold decrease in mean list length.

Fast gradient elution reversed-phase liquid chromatography with diode-array detection as a high-throughput screening method for drugs of abuse. II. Data analysis.

In Part I of this work, we developed a method for the detection of drugs of abuse in biological samples based on fast gradient elution liquid-chromatography coupled with diode array spectroscopic detection (LC-DAD). In this part of the work, we apply the chemometric method of target factor analysis (TFA) to the chromatograms. This algorithm identifies the target compounds present in chromatograms based on a spectral library, resolves nearly co-eluting components, and differentiates between drugs with similar spectra. The ability to resolve highly overlapped peaks using the spectral data afforded by the DAD is what distinguishes the present method from conventional library searching methods. Our library has a mean list length (MLL) of 1.255 and a discriminating power of 0.997 when both retention index and spectral factors are considered. The algorithm compares a library of 47 different compounds of toxicological relevance to unknown samples and identifies which compounds are present based on spectral and retention index matching. The application of a corrected retention index for identification rather than raw retention times compensates for long-term and column-to-column retention time shifts and allows for the use of a single library of spectral and retention data. Training data sets were used to establish the search and identification parameters of the method. A validation data set of 70 chromatograms was used to calculate the sensitivity (correct identification of positives) and specificity (correct identification of negatives) of the method, which were found to be 92% and 94%, respectively.