Buffering effects on the solution behavior and hydrolytic degradation of poly(β-amino ester)s

With a vast, synthetically accessible compositional space and highly tunable hydrolysis rates, poly(β-amino ester)s (PBAEs) are an attractive degradable polymer platform. Leveraging PBAEs in a wide range of applications hinges on the ability to program degradation, which, thus far, has been frustrated by multiple confounding phenomena contributing to the degradation of these charged polyesters. Basic conditions accelerate hydrolysis, yet reduce solubility, limiting water access to amines and esters. Further, the high buffering capacity of PBAEs can render buffers ineffective at controlling solution pH. To unify understanding of PBAE degradation and solution properties, this study examines PBAE hydrolysis as a function of pH and buffer concentration as well as polymer hydrophobicity. At low buffer concentrations, the PBAE amines and the acid produced during hydrolysis control solution pH. Meanwhile, at high buffer concentrations that afford relatively constant pH, hydrolysis rate increases with pH, despite the reduced PBAE solubility. Increasing the hydrophobic content of PBAEs eventually hinders the capacity of the polymer to accept protons from solution, limiting the pH increase and slowing hydrolysis. These studies showcase the role of buffering on the pH-dependent degradation and solution properties of PBAEs, providing guidance for programming degradation in applications ranging from drug delivery to thermosets.     

The Cytotoxic Effect of α-Synuclein Aggregates

Parkinson's disease is a neurodegenerative disorder involving a functional protein, α-synuclein, whose primary function is related to vesicle trafficking. However, α-synuclein is prone to form aggregates, and these inclusions, known as Lewy bodies, are the hallmark of Parkinson's disease. α-synuclein can alter its conformation and acquire aggregating capacity, forming aggregates containing β-sheets. This protein's pathogenic importance is based on its ability to form oligomers that impair synaptic transmission and neuronal function by increasing membrane permeability and altering homeostasis, generating a deleterious effect over cells. First, we establish that oligomers interfere with the mechanical properties of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) membrane, as demonstrated by nanoindentation curves. In contrast, nanoindentation revealed that the α-synuclein monomer's presence leads to a much more resistant lipid bilayer. Moreover, the oligomers’ interaction with cell membranes can promote lactate dehydrogenase (LDH) release, suggesting the activation of cytotoxic events.     

UPLC-Q/TOF-MS coupled with multivariate analysis for comparative analysis of metabolomic in Dendrobium nobile from different growth altitudes

Dendrobium nobile alkaloids (DNLA) and glycosides are the main active components extracted from Dendrobium nobile Lindl. (D. nobile) used for thousands of years in China. The pharmacological effects of the above chemical components are significantly different. D. nobile is mainly grown at an altitude ranging from 230 to 800 m in Chishui City, Northwest Guizhou Province. However, it is unclear whether the metabolite in D. nobile is influenced by the planting altitude. Hence, to reveal the different metabolite in D. nobile cultivated at the altitude of 336 m, 528 m, and 692 m, ultra-high performance liquid chromatography with Q/TOF-MS couple with multivariate analysis were developed. Using the orthogonal partial least squares-discriminant analysis, 19 different metabolites were discovered and then tentatively assigned their structures as alkaloids and glycosides by comparing mass spectrometry data with in-house database and literature. Moreover, the result of semiquantitative analysis showed the content of dendrobine that was belonged to alkaloids significantly increased at the altitude of 692 m, whereas the content of glycosides demonstrated an accumulation trend at the altitude of 528 m. The results could provide valuable information for the optimal clinical drug therapeutics and provide a reference for quality control.     

Kinetic model for Ostwald's rule of stages with applications to Boc-diphenylalanine self-assembly

A kinetic model which describes Ostwald's rule of stages, during the process of crystal growth from solution, is reported here. Reaction equations for stages are given where the stages convert from one to another. The final stage reacts to release a portion of solute back into solution, while the remainder converts to the final equilibrium form. Additionally, a remnant of the solute that was not consumed by any of the transitional stages, ultimately is converted into the final product. This particular model was motivated by a recent report for Boc-diphenylalanine self-assembly where the dissolved peptide was observed to go through two polymorphic stages before reaching the equilibrium supramolecular assembly [A. Levin et al., Nat. Commun. 5, 5219, (2014)]. Kinetic data for the concentration of solute present during the process are listed in the above-mentioned report. We show here how the model, for , describes the time-dependent behavior of the solute decay during the growth process. After comparing the model to the experimental data, we are able to report values for all of the rate constants and propose a rule whereby the relative magnitudes of these constants can be used to predict whether a supersaturated substance will noticeably pass through transitional stages or simply convert from solute to the equilibrium solid form.     

Ultra-high Tg and ultra-low coefficient of thermal expansion polyimide films based on hydrogen bond interaction

To tolerate high processing temperature during the fabrication of low-temperature polycrystalline silicon thin-film transistors (LTPS–TFT) in flexible OLED devices, the polyimide (PI) films, which are used as substrate, should have ultra-high glass transition temperature (T_g > 450°C) and ultra-low coefficient of thermal expansion (CTE at 0–5 ppm K⁻¹). In this paper, two novel heterocyclic monomers, namely, N,N'-(xanthone-2,7-diyl)bis(4-aminobenzamide) (p-DAXBA) and N,N'-(xanthone-2,7-diyl)bis(3-aminobenzamide) (m-DAXBA), which contain a xanthone moiety, are prepared and polycondensed with pyromellitic dianhydride (PMDA), respectively. PI films (PIa and PIb) with intrinsic high T_g and low CTE are designed from the perspective of rigid conjugate xanthone structure and hydrogen bonding interaction. It is found that the PIa films prepared by p-DAXBA have better linear structure of molecular chains and show relatively higher T_g and lower CTE. The T_g of PIa-40 is greater than 450°C, and CTE can reach as low as 2.7 ppm K⁻¹, tensile strength of 179 MPa, modulus of 5.67 GPa, indicating potential application prospect as a flexible OLED substrate.     

Dispersion and localisation in structured Rayleigh beams

This paper brings a comparative analysis between dynamic models of couple-stress elastic materials and structured Rayleigh beams on a Winkler foundation. Although physical phenomena have different physical origins, the underlying equations appear to be similar, and hence mathematical models have a lot in common. In the present work, our main focus is on the analysis of dispersive waves, band-gaps and localised waveforms in structured Rayleigh beams. The Rayleigh beam theory includes the effects of rotational inertia which are neglected in the Euler–Bernoulli beam theory. This makes the approach applicable to higher frequency regimes. Special attention is given to waves in pre-stressed Rayleigh beams on elastic foundations.     

Density functional theory study on sensing properties of g-C3N4 sheet to atmospheric gasses: Role of zigzag and armchair edges

The ability of the polymer-based graphitic carbon nitride (g-C₃N₄) as a gas sensor toward NO, NO₂, CO, CO₂, SO₂, SO₃, and O₂ gasses is assessed using density functional theory (DFT) calculations in terms of energetic and electronic transport characteristics. In particular, this study is aimed to explore the role of zigzag and armchair edges of the g-C₃N₄ sheet on sensing performances. The electronic properties of adsorption systems, such as Bader charge analysis, band gaps, work function, and density of states (DOS), are used to understand the interaction between the adsorbed gas molecules and the g-C₃N₄ sheet. Our calculated results indicate that SOx (SO₃ and SO₂) gasses have higher adsorption energies on the g-C₃N₄ sheet than other gasses. Furthermore, the transport properties, such as current–voltage (I-V) and resistance-voltage (R-V) curves along the zigzag and armchair directions are calculated using the non-equilibrium Green's function (NEGF) method to understand the performance of the g-C₃N₄ sheet as a prominent conductive/resistive sensor. The I-V/R-V results indicate that the zigzag g-C₃N₄ sheet has excellent sensing ability toward SOx gasses at low applied voltages. However, the presence of H₂O degrades the sensing performance of the armchair g-C₃N₄ sheet. Theoretical recovery time has also been calculated to evaluate the reusability of g-C₃N₄ sheet-based gas sensors. Our results reveal that the zigzag g-C₃N₄ sheet-based sensing device has a remarkably high sensitivity (>300%) and selectivity toward SOx gasses and has the potential to work in a complex environment.     

真实情境下问题解决的主题式教学设计与实施*——盖斯定律

当前“盖斯定律”的教学中,注重加和法、虚拟路径法等解题模型的教学,缺乏在真实情境中对物质转化及其能量关系的理解,学生无法感受到盖斯定律在生产中的价值。本文以“能量视角下煤的气化对于提高煤的燃烧效率的意义”为研究主题,通过分析建模、实验验证、情境回归等认识并应用盖斯定律,从能量视角再认识煤的气化对于提高煤的燃烧效率的意义,并且认识到利用化学反应可以实现对能量进行调控,如对工业废热的再利用,深化能量守恒观和能源节约意识,达成提升学科核心素养的目标。     

A Practical Approach for the Detection of Protein Tau with a Portable Potentiostat

Along with many factors, the change in protein tau isoforms, which has an obvious role in the function of microtubules, is an important biomarker of Alzheimer's disease. The aim of this study is to determine the protein Tau-441 with a portable potentiostat using a practical approach. For this purpose, screen printed electrodes (SPCEs) were first hydroxylated and then functional self-assembled monolayers were formed on the surface with 3-aminopropyltriethoxysilane (APTES). Evidence of anti-Tau being immobilized on to the surface was followed by techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FTIR). The constructed immunosensor showed a linear response within the concentration range of 0.0064–0.8 ng/mL for the target analyte Tau-441 and the limit of detection was found to be 0.0053 ng/mL. In addition, analytical behaviors such as reproducible measurements and storage life of the developed immunosensor with a portable potentiostat were also investigated. It has been demonstrated that Tau-441 can be captured with the help of portable device with sensitivity in CSF environment.     

The Story Behind the Link between Molecular Chirality and Crystal Shape

Here we describe the story behind the link between molecular chirality and macroscopic phenomena, the latter being a probe for the direct assignment of absolute configuration of chiral molecules. First, a brief tour of the history of molecular stereochemistry, starting with the classic experiment reported by Pasteur in 1848 on the separation of enantiomorphous crystals of a salt of tartaric acid, and his conclusion that the molecules of life are chiral of single-handedness. With time, this study raised, inter alia, two fundamental questions: the absolute configuration of chiral molecules and how a molecule of given configuration shapes the enantiomorphous morphology of its crystal. As for the first question, following the beginning of crystal structure determination by X-ray diffraction in 1912, it took almost 40 years before Bijvoet assigned molecular chirality through the esoteric method involving anomalous X-ray scattering. We have been able to address and link both questions through ‘everyday concepts of left and right’ (in the words of Jack Dunitz) by the use of ‘tailor-made’ auxiliaries. By such means, it proved possible to reveal, through morphology, etch patterns, epitaxy and symmetry reduction of both chiral and, paradoxically, centrosymmetric crystals, the basic chiral symmetry of the molecules of life, the α-amino acids and sugars.