Applying Direct Yellow 11 to a modified Simons’ staining assay

For quantification of overall fiber accessibility of lignocellulosic substrates, Direct Yellow 11 (C.I. 40000) is a suitable alternative to the discontinued Pylam Products’ dye Direct Orange 15 (C.I. 40002/40003). In this study we present a side-by-side comparison between the two azo-stilbene dyes. We characterize individual dye fractions and provide equations to determine individual concentrations. We present a modified Simons’ staining protocol incorporating the high molecular weight fraction of Direct Yellow 11. We perform tests on lignin, cellulosic, and lignocellulosic materials. In all tests, the two dyes perform similarly and satisfy many accessibility measurement criteria. We demonstrate that the adsorption of Direct Yellow 11 onto a substrate correlates with that substrate’s propensity for enzymatic hydrolysis. We confirm this correlation on a series of organic solvent pretreatments and on a series of lignocellulosic substrates. Finally, we outline the inherent limitations of performing adsorption experiments with Direct Yellow 11 and other high molecular weight dyes.     

Development of nanofibrillated cellulose coated with gold nanoparticles for measurement of melamine by SERS

The objective of this study was to develop nanofibrillated cellulose (NFC)-based substrate for rapid detection of melamine in milk by surface-enhanced Raman spectroscopy (SERS). NFC were served as a highly porous platform to load with gold nanoparticles (AuNPs), which can be used as a flexible SERS substrate with nanoscale roughness to generate strong electromagnetic field in SERS measurement. The NFC/AuNP substrate was characterized by UV–Vis spectroscopy and electron microscopy. Milk samples contaminated by different concentrations of melamine were measured by SERS coupled with NFC/AuNP substrate. The spectral data analysis was conducted by multivariate statistical analysis [i.e. partial least squares (PLS)]. Satisfactory PLS result for quantification of melamine in milk was obtained (R = 0.9464). The detection limit for melamine extracted from liquid milk by SERS is 1 ppm, which meets the World Health Organization’s requirement of melamine in liquid milk. These results demonstrate that NFC/AuNP substrate has improved homogeneity and can be used in SERS analysis for food safety applications.     

Thickness difference induced pore structure variations in cellulosic separators for lithium-ion batteries

The pore structure of the separator is crucial to the performance of a lithium-battery as it affects the cell resistance. Herein, a straightforward approach to vary the pore structure of Cladophora cellulose (CC) separators is presented. It is demonstrated that the pore size and porosity of the CC separator can be increased merely by decreasing the thickness of the CC separator by using less CC in the manufacturing of the separator. As the pore size and porosity of the CC separator are increased, the mass transport through the separator is increased which decreases the electrolyte resistance in the pores of the separator. This enhances the battery performance, particularly at higher cycling rates, as is demonstrated for LiFePO₄/Li half-cells. A specific capacity of around 100 mAh g^?1 was hence obtained at a cycling rate of 2 C with a 10 µm thick CC separator while specific capacities of 40 and close to 0 mAh g^?1 were obtained for separators with thicknesses of 20 and 40 µm, respectively. As the results also showed that a higher ionic conductivity was obtained for the 10 µm thick CC separator than for the 20 and 40 µm thick CC separators, it is clear that the different pore structure of the separators was an important factor affecting the battery performance in addition to the separator thickness. The present straightforward, yet efficient, strategy for altering the pore structure hence holds significant promise for the manufacturing of separators with improved performance, as well as for fundamental studies of the influence of the properties of the separator on the performance of lithium-ion cells.     

Synthesis and properties of novel stilbene-twelve alkyl quaternary ammonium salts as antibacterial optical whitening agents

Four novel stilbene-twelve alkyl quaternary ammonium salts 5a–d were synthesized. All synthesized compounds were characterized by FT-IR, ¹H-NMR and elemental analysis. Compounds 5a–d showed efficient whitening effect on cotton fiber and high fastness. Furthermore, compound 5c showed better stability to light than C186 in aqueous solution. The preliminary biological experiment demonstrated compounds 5a–d possessed significant antibacterial activities. Among them, compound 5d turned out to be the most active compound against Candida albicans with MIC₅₀ 4 μg/mL as well as E. coli with MIC₅₀ 16 μg/mL.     

Effects of mechanical stretching on average orientation of cellulose and pectin in onion epidermis cell wall: A polarized FT-IR study

The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm^?1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (ν_C=O, 1745 cm^?1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm^?1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development.     

Electrospun poly(ethylene oxide)/chitosan nanofibers with cellulose nanocrystals as support for cell culture of 3T3 fibroblasts

Chitosan/poly(ethylene oxide) (PEO) (5:1) nanofibers with cellulose nanocrystals (CNCs) were produced using an electrospinning technique. The addition of CNCs to the chitosan/PEO solutions allowed the production of uniform fibers (without beads) with a high proportion of chitosan. The fiber diameters were influenced by the concentration of CNCs in the chitosan/PEO solutions. The solutions containing 10% (w/w) of CNCs produced thinner fibers compared to solutions containing 5% (w/w) of CNCs. Thermogravimetric analysis indicated that the nanofibers were thermally stable, despite the CNCs having an effect on the PEO decomposition. Results from the cell assay in cultures of 3T3 fibroblasts indicated that the chitosan/PEO nanofibers (with 10% CNCs) promoted cell attachment with changes in the cytoskeletal organization. The results obtained in this work highlight the favorable effect of CNCs in electrospinning of chitosan/PEO. As expected, the influence of nanofibers on 3T3 fibroblasts F-actin and β-tubulin network revealed alterations in cytoskeleton, leading to changes in cell morphology and spreading.     

Measurement of the flexibility of wet cellulose fibres using atomic force microscopy

Flexibility and modulus of elasticity data for two types of wet cellulose fibres using a direct force–displacement method by means of AFM are reported for never dried wet fibres immersed in water. The flexibilities for the bleached softwood kraft pulp (BSW) fibres are in the range of 4–38 × 10¹² N^?1 m^?2 while the flexibilities for the thermomechanical pulp (TMP) fibres are about one order of magnitude lower. For BSW the modulus of elasticity ranges from 1 to 12 MPa and for TMP between 15–190 MPa. These data are lower than most other available pulp fibre data and comparable to a soft rubber band. Reasons for the difference can be that our measurements with a direct method were performed using never dried fibres immersed in water while other groups have employed indirect methods using pulp with different treatments.     

Novel hybrid process for the conversion of microcrystalline cellulose to value-added chemicals: part 2: effect of constant voltage on product selectivity

In this study, electrochemical degradation of microcrystalline cellulose (MCC) under hot-compressed water was investigated via application of constant voltage on reaction medium. Constant voltage ranges from 2.5 to 8.0 V was applied between anode (Titanium) and cathode (reactor wall). As an electrolyte and proton source 5–25 mM of H₂SO₄ was used. Reactions were carried out in a specially designed batch reactor (450 mL) made of T316 for 240 min at temperature of 200 °C.MCC decomposition products such as glucose, fructose, furfural, 5-HMF and levulinic acid were detected and quantified by High Performance Liquid Chromatography (HPLC). In the absence of electrolyte, applied voltage (2.5 and 4.0 V) decreased the total organic carbon (TOC) yield, in contrast at 8.0 V, TOC yield increased to 13%. Application of 8.0 V in hydrothermal conditions alter MCC decomposition pathway selectively to furfural (15%). Addition of electrolyte (5 mM, H₂SO₄) and application of 2.5 V potential increased TOC (54%) and changed the decomposition pathway in favor of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues of electrochemically reacted MCC was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by the application of constant voltage to reaction medium. In the presence of electrolyte, under certain voltage (2.5 V), functionalization of solid particles became more obvious in FTIR spectrum results. Therefore, change in the selectivity values of degradation products were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions.     

Bayesian molecular design with a chemical language model

The aim of computational molecular design is the identification of promising hypothetical molecules with a predefined set of desired properties. We address the issue of accelerating the material discovery with state-of-the-art machine learning techniques. The method involves two different types of prediction; the forward and backward predictions. The objective of the forward prediction is to create a set of machine learning models on various properties of a given molecule. Inverting the trained forward models through Bayes’ law, we derive a posterior distribution for the backward prediction, which is conditioned by a desired property requirement. Exploring high-probability regions of the posterior with a sequential Monte Carlo technique, molecules that exhibit the desired properties can computationally be created. One major difficulty in the computational creation of molecules is the exclusion of the occurrence of chemically unfavorable structures. To circumvent this issue, we derive a chemical language model that acquires commonly occurring patterns of chemical fragments through natural language processing of ASCII strings of existing compounds, which follow the SMILES chemical language notation. In the backward prediction, the trained language model is used to refine chemical strings such that the properties of the resulting structures fall within the desired property region while chemically unfavorable structures are successfully removed. The present method is demonstrated through the design of small organic molecules with the property requirements on HOMO-LUMO gap and internal energy. The R package iqspr is available at the CRAN repository.     

Blinded predictions of host-guest standard free energies of binding in the SAMPL5 challenge

In the context of the SAMPL5 blinded challenge standard free energies of binding were predicted for a dataset of 22 small guest molecules and three different host molecules octa-acids (OAH and OAMe) and a cucurbituril (CBC). Three sets of predictions were submitted, each based on different variations of classical molecular dynamics alchemical free energy calculation protocols based on the double annihilation method. The first model (model A) yields a free energy of binding based on computed free energy changes in solvated and host-guest complex phases; the second (model B) adds long range dispersion corrections to the previous result; the third (model C) uses an additional standard state correction term to account for the use of distance restraints during the molecular dynamics simulations. Model C performs the best in terms of mean unsigned error for all guests (MUE \(3.2\,<\,3.4\,<\,3.6\,\text{kcal}\,\text{mol}^{-1}\)—95 % confidence interval) for the whole data set and in particular for the octa-acid systems (MUE \(1.7\,<\,1.9\,<\,2.1\,\text{kcal}\,\text{mol}^{-1}\)). The overall correlation with experimental data for all models is encouraging (\(R^2\, 0.65\,<\,0.70<0.75\)). The correlation between experimental and computational free energy of binding ranks as one of the highest with respect to other entries in the challenge. Nonetheless the large MUE for the best performing model highlights systematic errors, and submissions from other groups fared better with respect to this metric.