Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H2

Lignin-rich stream from lignocellulosic ethanol production was converted into biocrude by continuous hydrothermal liquefaction (HTL) while hydrogen was produced by aqueous phase reforming (APR) of the HTL aqueous by-product. The effects of Na₂CO₃ and NaOH were investigated both in terms of processability of the feedstock as well as yield and composition of the obtained products. A maximum biocrude yield of 27 wt% was reached in the NaOH-catalyzed runs. A relevant amount of dissolved phenolics were detected in the co-produced aqueous phase (AP), and removed by liquid–liquid extraction using butyl acetate or diethyl ether, preserving the APR catalyst stability and reaching an hydrogen yield up to 146 mmol H₂ L⁻¹ AP. Preliminary mass balances integrating HTL and APR showed that the hydrogen provided by APR may account for up to 46% of the hydrogen amount theoretically required for upgrading the HTL biocrude, thus significantly improving the process performance and sustainability.     

The pseudo-single-phase,base-catalyzed transmethylation of soybean oil

The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and 1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0 wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results, presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical.     

Experimental study of the burner for FAA fire test: NexGen burner

The NexGen (Sonic) burner is the new burner developed by the Federal Aviation Administration, FAA, to replace old oil burners used for the required fire certification tests on power plant‐related materials, as it provides the capability to control both air and fuel flow rates. During a fire test, the burner is supposed to simulate a certain fire condition, so the flame properties should be robust and repeatable. The NexGen burner can achieve this due to the precise fuel and air controls. However, the current calibration criterion (ISO2685:1998 and AC20‐135) may not be good enough to ensure consistent flame properties. In the presented work, the sensitivity of the burner performance to air and fuel flow rate, as measured by the temperature and heat flux for calibration purposes, was studied. Additionally, the influence of the turbulator and the thermocouple size used for flame calibration was also studied. The impact of varying fuel/air ratio and thermocouple sizes was studied by conducting fire tests on aluminum samples, to show the inadequacies in the current calibration standards.     

A comparative study of new linear and hyperbranched polyurethanes built up from a synthesized isocyanate-terminated polyester/urethane

In the present study, the effects of architecture and structural building blocks of the polyurethane chains on their properties were studied. New linear and hyperbranched polyurethanes (LPU and HPU) were prepared via A2 + B2 and A2 + B3 methodologies, respectively. Polyethylene glycol (PEG-1000) and castor oil (CO) were used as bi- and trifunctional monomers (B2 and B3), respectively. However, A2 monomers were synthesized by the reaction between ethylene glycol (EG) with terephthaloyl chloride (TPC) and reacting the product with excess toluene diisocyanate (TDI) to produce isocyanate-terminated PU (NCO-PU). NCO-PU was reacted with PEG to synthesize LPU; however, its reaction with CO synthesized HPU. NCO-PU, LPU and HPU were characterized by FTIR, H-NMR, GPC, TEM, TGA, DSC and XRD. The prepared PUs were applied as coatings and their physical, chemical and mechanical properties were investigated. The results showed that the degree of branching of HPU was 79%. No phase separation was observed in NCO-PU as indicated by its DSC curve. However, two phases are detected in HPU and LPU that represent to the hard and soft segments. NCO-PU displayed the highest crystallinity index (CrI = 89.26%). However, the high degree of branching in HPU led to lower CrI than LPU. The lack of entanglements in HPU led to its slightly lower solution viscosity than LPU. TEM images showed spherical PU nano-particles. The surface of HPU coating showed the highest gloss which is due to its low degree of crystallinity. HPU and LPU exhibited excellent chemical resistivity.     

Significant Decline in Galactomannan Signal during Storage of Clinical Serum Samples

Galactomannan (GM) is widely used for detection of invasive aspergillosis in high-risk haemato-oncology patients. Recent publications have reported a lack of repeatability of GM detection. The objective of this retrospective study was to assess the repeatability of GM levels during storage of clinical samples. In a GM screening strategy, positive sera were repeat tested as per manufacturer’s recommendations. Short-term (ST) storage of samples was at +4 °C while long-term (LT) storage was at −80 °C. Bronchoalveolar (BAL) fluid was also repeating tested after ST storage and LT storage. Wilcoxon Signed Ranks Test was employed to assess the repeatability of GM levels. In a subset of 14 GM positive sera, repeat testing was performed on both the original serum and ethylenediaminetetraacetic acid (EDTA) pre-treated sample. There was a significant reduction in GM signals on repeat testing following ST storage (median GM index: 0.65 vs. 0.19; p < 0.001) and LT storage (median GM index: 0.56 vs. 0.10; p < 0.001) of serum samples. Of samples that were initially GM positive, an average GM index reduction of 50% was seen, with approximately two-thirds becoming GM negative on repeat testing of the same sample. In contrast, GM signal loss was not seen on repeat testing of BAL fluid following ST or LT storage. When GM positive serum samples were repeat tested using EDTA pre-treated serum from the first step of the testing protocol, all samples remained GM positive. In contrast, when the same samples were repeat tested from the original collected serum, 9 samples (64%) became GM negative. The significant reduction in GM signals during ST and LT storage of serum samples has implications for clinical management. Although the reasons for GM decline are unknown, they occur prior to the EDTA pre-treatment stage, indicating that the time from phlebotomy to testing should be minimized. BAL fluid GM index values remain stable.     

Host-Assisted Delivery of a Model Drug to Genomic DNA: Key Information from Ultrafast Spectroscopy and in silico Study

Drug delivery to a target without adverse effects is one of the major criteria for clinical use. Herein, we have made an attempt to explore the delivery efficacy of SDS surfactant in a monomer and micellar stage during the delivery of the model drug, Toluidine Blue (TB) from the micellar cavity to DNA. Molecular recognition of pre-micellar SDS encapsulated TB with DNA occurs at a rate constant of k₁ ∼652 s⁻¹. However, no significant release of encapsulated TB at micellar concentration was observed within the experimental time frame. This originated from the higher binding affinity of TB towards the nano-cavity of SDS at micellar concentration which does not allow the delivery of TB from the nano-cavity of SDS micelles to DNA. Thus, molecular recognition controls the extent of DNA recognition by TB which in turn modulates the rate of delivery of TB from SDS in a concentration-dependent manner.     

Prodynorphin and Proenkephalin in Cerebrospinal Fluid of Sporadic Creutzfeldt–Jakob Disease

Proenkephalin (PENK) and prodynorphin (PDYN) are endogenous opioid peptides mainly produced in the striatum and, to a lesser extent, in the cerebral cortex. Dysregulated metabolism and altered cerebrospinal fluid (CSF) levels of PENK and PDYN have been described in several neurodegenerative diseases. However, no study to date investigated these peptides in the CSF of sporadic Creutzfeldt–Jakob disease (sCJD). Using liquid chromatography-multiple reaction monitoring mass spectrometry, we evaluated the CSF PDYN- and PENK-derived peptide levels in 25 controls and 63 patients with sCJD belonging to the most prevalent molecular subtypes (MM(V)1, VV2 and MV2K). One of the PENK-derived peptides was significantly decreased in each sCJD subtype compared to the controls without a difference among subtypes. Conversely, PDYN-derived peptides were selectively decreased in the CSF of sCJD MV2K, a subtype with a more widespread overall pathology compared to the sCJD MM(V)1 and the VV2 subtypes, which we confirmed by semiquantitative analysis of cortical and striatal neuronal loss and astrocytosis. In sCJD CSF PENK and PDYN were associated with CSF biomarkers of neurodegeneration but not with clinical variables and showed a poor diagnostic performance. CSF PDYN and PENK-derived peptides had no significant diagnostic and prognostic values in sCJD; however, the distinct marker levels between molecular subtypes might help to better understand the basis of phenotypic heterogeneity determined by divergent neuronal targeting.     

Cefuroxime-impregnated calcium phosphates as an implantable delivery system in experimental osteomyelitis

The study aimed to investigate the effectiveness of porous calcium phosphates viz., hydroxyapatite (HAp) and a bi-phasic calcium phosphate (BCP) with predominately β-tricalcium phosphate (β-TCP) prepared by aqueous solution combustion method impregnated with cefuroxime axetil for the treatment of experimental osteomyelitis and compared with parenteral treatment. In vitro release of the drug was tested for its sustained elution characteristics for 21 days in PBS (pH 7.2) and measured by HPLC. In the in vivo study, bone infection was induced in tibia of rabbits by inoculation of 1 ml (3 × 10⁶) CFU Staphylococcus aureus. On the 21st day, after the development of osteomyelitis, six animals were treated by filling the cavity with cefuroxime-impregnated HAp blocks (Group II), six animals with the same drug-impregnated β-TCP (Group III) and in six others, only cefuroxime (15 mg/kg twice daily) was injected parenterally 6 weeks (Group IV). Group I with six animals was kept untreated. Histologically, the signs of infection were found to subside by 3 and 6 weeks. Radiological evaluation with cefuroxime-impregnated HAp and β-TCP pointed out the disappearance of sequestrum and existence of newly formed bony specules. Concentration of cefuroxime in bone and serum as estimated by HPLC showed highest value on day 21 itself which reduced marginally by day 42 in both the groups and these values were higher than minimum inhibitory concentration (MIC) against S. aureus. Our findings suggest that bi-phasic calcium phosphates with predominately β-TCP content is a very efficient carrier material for antibiotic compounds even for refractory infections by S. aureus.     

CFD simulations of the Andersen cascade impactor: Model development and effects of aerosol charge

Cascade impactors are commonly used to assess the size characteristics of aerosols in toxicology and pharmaceutical applications. These aerosol instruments have been developed and refined over decades. However, a number of questions remain related to impactor performance, including the influence of electrostatic charge on measured size distributions. The objective of this study was to develop a validated CFD model of the Mark II Andersen cascade impactor (ACI) and apply this model to evaluate the effects of particle charge on deposition. The flow field was simulated using a commercial CFD code for incompressible laminar and transitional flows. Particle trajectories and deposition were evaluated using a well tested Lagrangian tracking approach that accounts for impaction, sedimentation, diffusion, and electrostatic attraction. Particle charge levels typical of dry powder inhaler (DPI) and metered dose inhaler (MDI) aerosols were considered for a particle size range of 0.3–12 μm. As a model validation, computational predictions of cutoff d₅₀ diameters for each of the eight ACI stages were found to be within 10% difference of existing experimental and manufacturer data. Results indicated that charges consistent with DPI and MDI aerosols increased deposition fraction in Stages 0–3 by up to 30% and increased deposition fraction in Stages 4–7 by up to an order of magnitude. For Stages 0–3, both DPI and MDI charges reduced the d₅₀ value by approximately 10% or less. In contrast, charged aerosols reduced the d₅₀ values in Stages 4 and 5 by 200% and 60%, respectively. All charged submicrometer aerosols considered deposited in Stages 6 and 7. Increasing the particle charge by an order of magnitude from DPI to MDI values had a relatively small effect on further decreasing the cutoff size of each stage. In conclusion, these results can be used to approximate the actual aerodynamic diameter of a charged pharmaceutical aerosol based on measurements in a standard ACI. Future applications of the developed ACI model include evaluating the influence of space charge on deposition and quantifying the effects of aerosol condensation and evaporation on size assessment.     

Identification of trinucleotide repeat ligands with a FRET melting assay

DNA hairpin structures formed within a repeated tract might be a causative factor for triplet expansion observed in several debilitating diseases. We have designed and used a fluorescence resonance energy transfer (FRET) melting assay to screen for ligands that bind specifically to the CNG triplet repeats. Using this assay, we screened a panel of 33 chemicals that were previously designed to bind DNA or RNA secondary structures. Remarkably, we found that macrocyclic compounds, such as acridine dimers and trimers, exhibit interesting affinities and specificities for this motif.