Porous Perovskite Fibers – Preparation by Wet Phase Inversion Spinning and Catalytic Activity

Porous perovskite (LaMnO₃) fibers were prepared by means of wet phase inversion spinning. The influence of different spinning procedures, slurry and coagulation bath composition on fiber shape and pore morphology was studied. The catalytic activity of the prepared fibers was tested for carbon monoxide oxidation as a model reaction in a differential recycle reactor. The results revealed that by suitable choice of process conditions porous catalytically active fibers can be prepared. Catalytic measurements confirmed that the catalytic fibers exhibit an open structure that allows full utilization of the catalytically active surface without intraparticle diffusional limitations.     

Real time monitoring of bioreactor mAb IgG3 cell culture process dynamics via Fourier transform infrared spectroscopy: Implications for enabling cell culture process analytical technologyŽ 

Compared to small molecule process analytical technology (PAT) applications, biotechnology product PAT applications have certain unique challenges and opportunities. Understanding process dynamics of bioreactor cell culture process is essential to establish an appropriate process control strategy for biotechnology product PAT applications. Inline spectroscopic techniques for real time monitoring of bioreactor cell culture process have the distinct potential to develop PAT approaches in manufacturing biotechnology drug products. However, the use of inline Fourier transform infrared (FTIR) spectroscopic techniques for bioreactor cell culture process monitoring has not been reported. In this work, real time inline FTIR Spectroscopy was applied to a lab scale bioreactor mAb IgG3 cell culture fluid biomolecular dynamic model. The technical feasibility of using FTIR Spectroscopy for real time tracking and monitoring four key cell culture metabolites (including glucose, glutamine, lactate, and ammonia) and protein yield at increasing levels of complexity (simple binary system, fully formulated media, actual bioreactor cell culture process) was evaluated via a stepwise approach. The FTIR fingerprints of the key metabolites were identified. The multivariate partial least squares (PLS) calibration models were established to correlate the process FTIR spectra with the concentrations of key metabolites and protein yield of in-process samples, either individually for each metabolite and protein or globally for all four metabolites simultaneously. Applying the 2^nd derivative pre-processing algorithm to the FTIR spectra helps to reduce the number of PLS latent variables needed significantly and thus simplify the interpretation of the PLS models. The validated PLS models show promise in predicting the concentration profiles of glucose, glutamine, lactate, and ammonia and protein yield over the course of the bioreactor cell culture process. Therefore, this work demonstrated the technical feasibility of real time monitoring of the bioreactor cell culture process via FTIR spectroscopy. Its implications for enabling cell culture PAT were discussed.     

Changes in Molecular Characteristics of Cereal Carbohydrates after Processing and Digestion

Different extraction, purification and digestion methods were used to investigate the molecular properties of carbohydrates in arabinoxylan and β-glucan concentrates, dietary fiber (DF) rich breads and ileum content of bread fed pigs. The breads studied were: a low DF wheat bread (WF), whole meal rye bread (GR), rye bread with kernels (RK), wheat bread supplemented with wheat arabinoxylan concentrate (AX) and wheat bread supplemented with oat β-glucan concentrate (BG). The weight average molecular weight (M_w) of extractable carbohydrates in β-glucan concentrate decreased eight-fold after inclusion in the BG bread when exposed to in vitro digestion, while the M_w of purified extractable carbohydrates in AX bread was reduced two-fold, and remained almost unaffected until reaching the terminal ileum of pigs. Similarly, the M_w of purified extractable carbohydrates in GR and RK bread was not significantly changed in the ileum. The AX bread resulted in the highest concentration of dissolved arabinoxylan in the ileum among all the breads that caused a substantial increased in ileal AX viscosity. Nevertheless, for none of the breads, the M_w of extractable carbohydrates was related neither to the bread extract nor ileal viscosity.     

Electrophoretic deposition of carbon nanotubes onto carbon-fiber fabric for production of carbon/epoxy composites with improved mechanical properties

Carbon nanotubes (CNTs) have been deposited onto carbon-fiber fabric using electrophoretic deposition (EPD) prior to the infusion of epoxy resin for the production of carbon/epoxy composites. The carbon-fiber fabric employed for EPD was used in the as-received condition, in which the proprietary epoxy sizing-agent was present. CNTs were functionalized prior to EPD using ozone treatment for oxidation, followed by chemical reaction with polyethyleneimine. The CNT oxidation used a novel recirculating system which enabled ozonolysis to be conducted on large-volume solutions of CNTs in the presence of high-powered sonication, facilitating preparation of stable dispersions suitable for EPD. Significant increases in the shear strength and fracture toughness of the carbon/epoxy composites with the CNT treatment have been measured relative to composites without the CNT treatment. Analysis of fracture surfaces revealed interlaminar regions with high levels of CNTs and evidence of good adhesion between the carbon nanotubes and sized carbon-fiber, which is believed to have contributed to the measured improvement in mechanical properties.     

Development of a Bio-Inspired Dual Catalytic System for Alkane Dehydrogenation

The alkene is a central functional group in organic synthesis. While myriad reliable methods exist to access this moiety from other functionalities, acceptorless dehydrogenation, or the direct synthesis of alkenes from alkanes with hydrogen gas as the sole byproduct, remains a challenging, albeit highly desirable, transformation. This essay provides an account of our recent efforts toward accessing this difficult reaction class, with particular attention paid to the diverse precedents that informed our explorations. This report highlights the benefits of maintaining a broad range of interests, and we hope that it illustrates the vast connectivity between chemical disciplines.     

Fox Hunting in Wild Apples: Searching for Novel Genes in Malus Sieversii

Malus sieversii is considered the progenitor of modern apple (Malus pumila) cultivars and to represent a valuable source of genetic diversity. Despite the importance of M. sieversii as a source of disease resistance, stress tolerance, and novel fruit traits, little is known about gene function and diversity in M. sieversii. Notably, a publicly annotated genome sequence for this species is not available. In the current study, the FOX (Full-length cDNA OvereXpressing) gene hunting system was used to construct a library of transgenic lines of Arabidopsis in which each transgenic line overexpresses a full-length gene obtained from a cDNA library of the PI619283 accession of M. sieversii. The cDNA library was constructed from mRNA obtained from bark tissues collected in late fall–early winter, a time at which many abiotic stress-adaptative genes are expressed. Over 4000 apple FOX Arabidopsis lines have been established from the pool of transgenic seeds and cDNA inserts corresponding to various Gene Ontology (GO) categories have been identified. A total of 160 inserts appear to be novel, with no or limited homology to M. pumila, Arabidopsis, or poplar. Over 1300 lines have also been screened for freezing resistance. The constructed library of transgenic lines provides a valuable genetic resource for exploring gene function and diversity in Malus sieversii. Notably, no such library of t-DNA lines currently exists for any Malus species.     

Temperature-Dependent Re-alignment of the Short Multifunctional Peptide BP100 in Membranes Revealed by Solid-State NMR Spectroscopy and Molecular Dynamics Simulations

BP100 is a cationic undecamer peptide with antimicrobial and cell-penetrating activities. The orientation of this amphiphilic α-helix in lipid bilayers was examined under numerous conditions using solid-state ¹⁹F, ¹⁵N and ²H NMR. At high temperatures in saturated phosphatidylcholine lipids, BP100 lies flat on the membrane surface, as expected. Upon lowering the temperature towards the lipid phase transition, the helix is found to flip into an upright transmembrane orientation. In thin bilayers, this inserted state was stable at low peptide concentration, but thicker membranes required higher peptide concentrations. In the presence of lysolipids, the inserted state prevailed even at high temperature. Molecular dynamics simulations suggest that BP100 monomer insertion can be stabilized by snorkeling lysine side chains. These results demonstrate that even a very short helix like BP100 can span (and thereby penetrate through) a cellular membrane under suitable conditions.     

Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols

3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R,11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of -butyrolactones by using different alkyl lithiums as nucleophiles.     

Equilibrium Studies of the System'(Fe,Co)O'–(Fe,Co)3O4 by Solid-State emf Measurements in the Temperature Range 970 to 1370 K

The equilibrium reaction 3'(Fe, Co)O'( ss ) +1/2O₂ ( g ) ⇄ (Fe, Co)₃O₄( ss ) was studied in the temperature range 970 to 1370 K for seven different total compositions of molar ratios 0.5 < Fe/(Fe + Co) ≤ 1.0. The equilibrium pressures of oxygen were determined by using galvanic cells incorporating calcia stabilized zirconia as solid electrolyte and the Fe/Co ratios in the solid-solution phases by wavelength dispersive spectrometry microprobe analyses. The activities of 'FeO' in the cobaltowüstite phase were then derived from the experimental results obtained.