Lignin, extractives and structural carbohydrate characteristics of Thinopyrum intermedium biomass reveal additional valorization opportunities for dual-crop utilization.

Background: Thinopyrum intermedium (Host) Barkworth & D.R. Dewey, or intermediate wheat grass (IWG), is being developed as the first widely-available perennial grain candidate.

Application of lithium cationization tandem mass spectrometry for structural analysis of lignin model oligomers with β-β' and β-O-4' linkages.

Structural elucidation of lignin degradation products is a requirement for successfully developing lignin valorization technology. Most of mass spectrometry-based techniques have utilized negative ion mode mass spectrometry for structural elucidation of lignin-derived compounds. Unfortunately, simple deprotonation can lead to in-source fragmentation and may not be suitable for condensed lignin structures without acidic moieties.

Strategy for Conjugating Oligopeptides to Mesoporous Silica Nanoparticles Using Diazirine-Based Heterobifunctional Linkers.

Successful strategies for the attachment of oligopeptides to mesoporous silica with pores large enough to load biomolecules should utilize the high surface area of pores to provide an accessible, protective environment. A two-step oligopeptide functionalization strategy is examined here using diazirine-based heterobifunctional linkers. Mesoporous silica nanoparticles (MSNPs) with average pore diameter of ~8 nm and surface area of ~730 m/g were synthesized and amine-functionalized.

Complexation of Lignin Dimers with β-Cyclodextrin and Binding Stability Analysis by ESI-MS, Isothermal Titration Calorimetry, and Molecular Dynamics Simulations.

Lignin derived from lignocellulosic biomass is the largest source of renewable bioaromatics present on earth and requires environmentally sustainable separation strategies to selectively obtain high-value degradation products. Applications of supramolecular interactions have the potential to isolate lignin compounds from biomass degradation fractions by the formation of variable inclusion complexes with cyclodextrins (CDs). CDs are commonly used as selective adsorbents for many applications and can capture guest molecules in their internal hydrophobic cavity.

Using Pet Therapy to Decrease Patients' Anxiety on Two Diverse Inpatient Units.

Background: The physical benefits for patients who spend time with a therapy dog have been reported, including decreased anxiety. Pet therapy has decreased anxiety in various hospitalized patient populations. The human-animal bond is the foundation for the positive interaction therapy dogs create.

Target-directed evolution of novel modulators of the dopamine transporter in Lobelia cardinalis hairy root cultures.

The dopamine transporter (DAT) is targeted in substance use disorders (SUDs), and "non-classical"" DAT inhibitors with low abuse potential are therapeutic candidates. Lobinaline, from Lobelia cardinalis, is an atypical DAT inhibitor lead. Chemical synthesis of lobinaline is challenging; thus, "target-directed evolution" was used for lead optimization.

Pharmacokinetic and metabolic analysis of an Alzheimer's disease therapeutic in rat serum via microfluidic CZE-MS.

Sensitive, high-throughput methods for pharmacokinetic (PK) profiling are essential for potential therapeutics during critical stages of clinical trials. The application of a microfluidic capillary zone electrophoresis mass spectrometry (CZE-MS) method for PK profiling allows for rapid, sensitive and in-depth analysis of multiple samples within a short timeframe. Here, a CZE-MS approach for PK analysis was compared with a traditional UHPLC-MS approach when analyzing serum extracts from rats treated with a potential Alzheimer's disease therapeutic, BNC-1.

Interaction of lignin dimers with model cell membranes: A quartz crystal microbalance and molecular dynamics simulation study.

A study of the interaction between cell membranes and small molecules derived from lignin, a protective phenolic biopolymer found in vascular plants, is crucial for identifying their potential as pharmacological and toxicological agents. In this work, the interactions of model cell membranes [supported 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers] are compared for three βO4 dimers of coniferyl alcohol (G lignin monomer): guaiacylglycerol guaiacol ester with a hydroxypropenyl (HOCH-) tail (G-βO4'-G), a truncated GG dimer without HOCH- (G-βO4'-truncG), and a benzylated GG dimer (benzG-βO4'-G). The uptake of the lignin dimers (per mass of lipid) and the energy dissipation (a measure of bilayer disorder) are higher for benzG-βO4'-G and G-βO4'-truncG than those for G-βO4'-G in the gel-phase DPPC bilayer, as measured using quartz crystal microbalance with dissipation (QCM-D).

The study of the chromatographic behavior and a mass spectrometric approach to differentiating the diastereomer pair of the β-O-4 lignin dimer series.

Lignin and lignans are natural products found in plant cell walls. Lignin research has historically focused on lignin degradation techniques in the hope of converting lignin into useful aromatic carbon feedstocks. In contrast, investigations of lignans existing as natural product dimers, have been focused on thier interesting biological activities.

Experimental and Molecular Dynamics Simulation Study of the Effects of Lignin Dimers on the Gel-to-Fluid Phase Transition in DPPC Bilayers.

High resolution differential scanning calorimetry (DSC) and molecular dynamics (MD) simulations were used to investigate the effect of three lignin dimers on the gel to fluid phase transition in DPPC lipid bilayers. The goal of this research is to begin to understand the partitioning of model lignin dimers into lipid bilayers and its effects on the gel to fluid transition temperature (). The long-term objective is to establish structure-function relationships for well-defined lignin derivatives at biologically relevant surfaces.

Microfluidic capillary zone electrophoresis mass spectrometry analysis of alkaloids in Lobelia cardinalis transgenic and mutant plant cell cultures.

Application of a microfluidic CE device for CZE-MS allows for fast, rapid, and in-depth analysis of large sample sets. This microfluidic CZE-MS device, the 908 Devices ZipChip, involves minimal sample preparation and is ideal for small cation analytes, such as alkaloids. Here, we evaluated the microfluidic device for the analysis of alkaloids from Lobelia cardinalis hairy root cultures.

Modulating Mechanical Properties of Collagen-Lignin Composites.

Three-dimensional matrices of collagen type I (Col I) are widely used in tissue engineering applications for its abundance in many tissues, bioactivity with many cell types, and excellent biocompatibility. Inspired by the structural role of lignin in a plant tissue, we found that sodium lignosulfonate (SLS) and an alkali-extracted lignin from switchgrass (SG) increased the stiffness of Col I gels. SLS and SG enhanced the stiffness of Col I gels from 52 to 670 Pa and 52 to 320 Pa, respectively, and attenuated shear-thinning properties, with the formulation of 1.

A comparative study of the electrospray ionization response of β-O-4' lignin model compounds.

Electrospray ionization mass spectrometry has recently become the technique of choice for rapid characterization of lignin degradation products. However, the fundamental question of the relationship between lignin structure and ionization efficiency has not been explored. In this work, we studied the electrospray ionization response of five structurally similar β-O-4' model lignin compounds using lithium cationization in the positive electrospray ionization mode.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis for characterization of lignin oligomers using cationization techniques and 2,5-dihydroxyacetophenone (DHAP) matrix.

Rationale: Effective analytical techniques are needed to characterize lignin products for the generation of renewable carbon sources. Application of matrix-assisted laser desorption/ionization (MALDI) in lignin analysis is limited because of poor ionization efficiency. In this study, we explored the potential of cationization along with a 2,5-dihydroxyacetophenone (DHAP) matrix to characterize model lignin oligomers.

Characterization and sequencing of lithium cationized β-O-4 lignin oligomers using higher-energy collisional dissociation mass spectrometry.

The prospect of developing new bio-based products from lignin partially depends on the development of effective analytical techniques to characterize the end products from lignin degradation experiments. To date, the most utilized mass spectrometric technique for characterizing lignin oligomers has been negative ion mass spectrometry. Positive ion mass spectrometry remains a relatively unexplored approach for lignin sequencing.

A novel method for the rapid detection of post-translationally modified visinin-like protein 1 in rat models of brain injury.

Background: Although elevated serum levels of visinin-like protein 1 (VILIP-1), a neuron-specific calcium sensor protein, are associated with ischaemic stroke, only a single study has evaluated VILIP-1 as a biomarker of traumatic brain injury (TBI). The current proof-of-concept study was designed to determine whether serum VILIP-1 levels increase post-injury in a well-characterized rat unilateral cortical contusion model.

Methods: Lateral flow devices (LFDs) rapidly (< 20 min) detected trace serum levels (pg/mL) of VILIP-1 in a small input sample volume (10 µL).

Correlating the potentiometric selectivity of cyclosporin-based electrodes with binding patterns obtained from electrospray ionization-mass spectrometry.

Electrospray ionization mass spectrometry ESI-MS is a powerful technique for the characterization of macromolecules and their noncovalent binding with guest ions. We herein evaluate the feasibility of using ESI-MS as a screening tool for predicting potentiometric selectivities of ionophores. Ion-selective electrodes based on the cyclic peptide, cyclosporin A, were developed, and their potentiometric selectivity pattern was evaluated.

A Novel Small Molecule Modulator of Amyloid Pathology.

Because traditional approaches to drug development for Alzheimer's disease are becoming increasingly expensive and in many cases disappointingly unsuccessful, alternative approaches are required to shift the paradigm. Following leads from investigations of dihydropyridine calcium channel blockers, we observed unique properties from a class of functionalized naphthyridines and sought to develop these as novel therapeutics that minimize amyloid pathology without the adverse effects associated with current therapeutics. Our data show methyl 2,4-dimethyl-5-oxo-5,6-dihydrobenzo[c][2,7]naphthyridine-1-carboxylate (BNC-1) significantly decreases amyloid burden in a well-established mouse model of amyloid pathology through a unique mechanism mediated by Elk-1, a transcriptional repressor of presenilin-1.

A Novel Plasma Based Biomarker of Alzheimer's Disease.

Specific biomarkers in a readily accessible biological fluid, such as blood, could aid in the identification, characterization, validation, and routine monitoring of Alzheimer's disease (AD) progression. In the current study, levels of the previously described novel cerebrospinal fluid aberrant protein complex composed of prostaglandin-D-synthase (PDS) and transthyretin (TTR) were quantified in plasma by a custom two-probe sandwich ELISA and compared to amyloid-β (Aβ)(1-42) as a standard plasma biomarker of AD. Plasma was analyzed from 140 probable AD subjects, 135 subjects with mild cognitive impairment (MCI), 74 normal control subjects (NC) prior to MCI transition, 23 diseased control (DC) subjects with either frontotemporal dementia or dementia with Lewy bodies, and 182 normal control (NC) subjects who did not progress to MCI or dementia.

Calcium Channel Blockers, Progression to Dementia, and Effects on Amyloid Beta Peptide Production.

Previous epidemiologic studies suggest that antihypertensive drugs may be protective against cognitive decline. To determine if subjects enrolled in the University of Kentucky longitudinal aging study who used antihypertensive drugs showed diminished progression to dementia, we used a 3-parameter logistic regression model to compare the rate of progression to dementia for subjects who used any of the five common categories of antihypertensive drugs to those with similar demographic characteristics but who did not use antihypertensives. Regression modeling showed that subjects who used calcium channel blockers (CCBs) but not the other classes of antihypertensives showed a significant decrease in the rate of progression to dementia.

Pretreatment of lignocellulosic biomass using Fenton chemistry.

In an attempt to mimic white-rot fungi lignin degradation via in vivo Fenton chemistry, solution phase Fenton chemistry (10 g biomass, 176 mmol hydrogen peroxide and 1.25 mmol Fe(2+) in 200 mL of water) was applied to four different biomass feedstocks. An enzymatic saccharification of Fenton pretreated biomass showed an average 212% increase relative to untreated control across all four feedstocks (P<0.

Nucleic acid oxidation: an early feature of Alzheimer's disease.

Studies of oxidative damage during the progression of Alzheimer's disease (AD) suggest its central role in disease pathogenesis. To investigate levels of nucleic acid oxidation in both early and late stages of AD, levels of multiple base adducts were quantified in nuclear and mitochondrial DNA from the superior and middle temporal gyri (SMTG), inferior parietal lobule (IPL), and cerebellum (CER) of age-matched normal control subjects, subjects with mild cognitive impairment, preclinical AD, late-stage AD, and non-AD neurological disorders (diseased control; DC) using gas chromatography/mass spectrometry. Median levels of multiple DNA adducts in nuclear and mitochondrial DNA were significantly (p ≤ 0.