Designer Self-Assembling Peptide Materials for Diverse Applications

Summary: Macromolecuar chemistry and polymer science have had an enormous impact in many areas of science, engineering, medicine and our daily life. It has not only changed our way of life forever, but also continuously to improve our living standard. Macromolecuar chemistry now also encompasses bioengineering, biomimetics, designer biological materials and nanobiotechnology. Here we summarize a few classes of short peptides that we discovered and invented with broad applications including 3D tissue cell culture, reparative and regenerative medicine, tissue engineering, slow drug release, stabilization of membrane proteins for develop nanobiotechnology and molecular devices. Molecular design using short peptides as new materials will play increasingly important role in biomedical research, nanobiotechnology, clinical science and medicine.     

Temporal onset-order discrimination through the tactual sense: effects of frequency and site of stimulation

This research extends the study of temporal resolution of the tactual sensory system through measurements of temporal-onset order discrimination for continuous tonal signals addressing (a) the effects of frequency separation of the two stimuli whose onset orders are to be discriminated and (b) the effects of redundant coding of frequency and site of stimulation on performance. Sinusoidal signals were presented either at two separate digits (thumb and index finger of the left hand) or at a single site of stimulation (left index finger) using a multifinger tactual stimulation system. Measurements were obtained using a one-interval two-alternative forced choice procedure in which each interval consisted of the random-order presentation of two different stimuli with roving values of amplitude and duration. Thresholds were estimated from psychometric functions of d' as a function of stimulus-onset asynchrony (SOA). On average, temporal onset-order thresholds were larger for one-finger conditions (mean SOA of 74.8 ms) than for two-finger conditions (mean SOA of 48.5 ms) and decreased as frequency separation increased, particularly for single-site presentation. Redundant coding of frequency and site of stimulation resulted in higher resolution by a factor of 1.5 compared to frequency alone and by a factor of 1.2 compared to site alone.     

Structural and photophysical studies of phenanthrene adducts involving C6F5HgCl and [o-C6F4Hg]3

Both pentafluorophenylmercury chloride and trimeric perfluoro-ortho-phenylene mercury interact with phenanthrene to form phosphorescent adducts which exhibit extended binary stacks in the solid state.     

Dual Electroactivity in a Covalent Organic Network with Mechanically Interlocked Pillar[5]arenes

The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material.     

Temporal onset-order discrimination through the tactual sense

Tactual temporal-onset order thresholds were measured for two sinusoidal vibrations of different frequencies delivered to two separate locations (thumb and index finger) of a multi-finger tactual stimulating device. The frequency delivered to the thumb was fixed at 50 Hz and that to the index finger at 250 Hz. The amplitude and duration of each of the two sinusoidal vibrations were roved independently from trial to trial in a 1-interval, 2AFC procedure. Performance, measured as a function of stimulus-onset asynchrony (SOA), indicated that the temporal-onset-order threshold averaged 34 ms across four subjects. The data were further classified into subsets according to both the amplitude and duration of the two stimuli in each trial of the roving-discrimination paradigm. The results indicated that the amplitude differences of the two stimuli in each trial had a substantial effect on onset-order discrimination, while duration differences generally had little effect. The effects of amplitude differences are explained qualitatively in terms of amplitude latency relationships and stimulus interactions such as temporal masking. Overall, the results not only contribute to an enhanced understanding of the temporal sensitivity of the tactual system but also provide guidelines for the design of tactual aids for hearing-impaired persons.     

Chemistry and electrochemistry of lithium iron phosphate

We report here several synthesis routes and their respective drawbacks/advantages for the preparation of pure LiFePO₄. We demonstrate the possibility of using LiFePO₄ for electrochemical applications, with respect that an effective carbon coating was realized onto the smallest particles. Actually, to bypass the weak ionic conductivity of lithium iron phosphate, the thinnest would be the particles; the highest would be the performance under severe electrochemical conditions.     

A mass spectrometric study on meloxicam metabolism in horses and the fungus Cunninghamella elegans,and the relevance of this microbial system as a model of drug metabolism in the horse

This paper describes a study where the metabolism of the non‐steroidal anti‐inflammatory drug meloxicam was investigated in six horses and in the filamentous fungus Cunninghamella elegans. The metabolites identified were compared between the species, and then the fungus was used to produce larger amounts of the metabolites for future use as reference material. C. elegans proved to be a good model of phase I meloxicam metabolism in horses since all four metabolites found were the same in both species. Apart from the two main metabolites, 5′‐hydroxymethylmeloxicam and 5′‐carboxymeloxicam, a second isomer of hydroxymeloxicam and dihydroxylated meloxicam were detected for the first time in horse urine and the microbial incubations. Phase II metabolites were not discovered in the C. elegans samples but hydroxymeloxicam glucuronide was detected intact in horse urine for the first time in this study. Urine from six horses was further analyzed in a semi‐quantitative sense and 5′‐hydroxymethylmeloxicam gave peaks with much higher intensity compared to the parent drug and the other metabolites, and was detected for at least 14 days after the last given dose in some of the horses. From the results presented in this article, we suggest that analytical methods developed for the detection of meloxicam in horse urine after prohibited use should focus on the 5′‐hydroxymethyl metabolite and that C. elegans can be used to produce large amounts of this metabolite for potential future use as a reference compound. Copyright © 2009 John Wiley & Sons, Ltd.     

An improved detailed chemical kinetic model for C3-C4 linear and iso-alcohols and their blends with gasoline at engine-relevant conditions

Propanol and butanol isomers have received significant research attention as promising fuel additives or neat biofuels. Robust chemical kinetic models are needed that can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions. This study seeks to improve the understanding of ignition and combustion behavior of pure C3-C4 linear and iso-alcohols, and their blends with gasoline at engine-relevant conditions. In this work, a kinetic model with improved thermochemistry and reaction kinetics was developed based on recent theoretical calculations of H-atom abstraction and peroxy radical reaction rates. Kinetic model validations are reported, and the current model reproduces the ignition delay times of the C3 and C4 alcohols well. Variations in reactivity over a wide range of temperatures and other operating conditions are also well predicted by the current model. Recent ignition delay time measurements from a rapid compression machine of neat iso-propanol and iso-butanol [Cheng et al., Proc. Combust Inst. (2020)] and blends with a research grade gasoline [Goldsborough et al., Proc. Combust Inst. (2020)] at elevated pressure (20–40 bar) and intermediate temperatures (780–950 K) were used to demonstrate the accuracy of the current kinetic model at conditions relevant to boosted spark-ignition engines. The effects of alcohol blending with gasoline on the autoignition behavior are discussed. The current model captures the suppression of reactivity in the low-temperature and negative-temperature-coefficient (NTC) region when either isopropanol and isobutanol are added to a research grade gasoline. Sensitivity and reaction flux analysis were performed to provide insights into the relevant fuel chemistry of the C3-C4 alcohols.     

Nanostructured nonionic thymidine nucleolipid self-assembly materials

Three nucleoside lipids have been synthesized: 3'-oleoylthymidine, 3',5'-dioleoylthymidine, and 3'-phytanoylthymidine. Differential scanning calorimetry and X-ray diffraction have been employed to characterize the physical properties of these neat lipids. Polarizing optical microscopy, small-angle X-ray scattering, and cryo-transmission electron microscopy techniques have been used to investigate the phase behavior in aqueous systems. Both oleoyl-based nucleoside lipids adopted a lamellar crystalline phase in the neat form at room temperature, and the phytanoyl derivative exhibited a fluid isotropic phase. Under excess water conditions, the presence of one branched (phytanoyl) or one unsaturated (oleoyl) chain promoted the formation of a liquid-crystalline lamellar phase at physiological temperatures. In contrast, the 3',5'-dioleoylthymidine derivative is nonswelling and does not exhibit lyotropic liquid-crystalline phase behavior. The nucleolipids' propensity for DNA-type binding and recognition has been evaluated by using a monolayer system to measure surface pressure-area isotherms in a Langmuir trough and indicates that the nucleoside base is available for nonspecific hydrogen bonding in the monolayer liquid expanded state for the single-chain nucleolipids but not for the dual-chain amphiphile.     

A Phase Field Approach for Martensitic Transformations and Crystal Plasticity

This work is motivated by cryogenic turning which allows end shape machining and simultaneously attaining a hardened surface due to deformation induced martensitic transformations. To study the process on the microscale, a multivariant phase field model for martensitic transformations in conjunction with a crystal plastic material model is introduced. The evolution of microstructure is assumed to follow a time-dependent Ginzburg-Landau equation. To solve the field equations the finite element method is used. Time integration is performed with Euler backward schemes, on the global level for the evolution equation of the phase field, and on the element level for the crystal plastic material law. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)