What is the form of muscimol from fly agaric mushroom (Amanita muscaria) in water? An insight from NMR experiment supported by molecular modeling

The biologically active alkaloid muscimol is present in fly agaric mushroom (Amanita muscaria), and its structure and action is related to human neurotransmitter _γ-aminobutyric acid (GABA). The current study reports on determination of muscimol form present in water solution using multinuclear ¹H and ¹³C nuclear magnetic resonance (NMR) experiments supported by density functional theory molecular modeling. The structures of three forms of free muscimol molecule both in the gas phase and in the presence of water solvent, modeled by polarized continuous model, and nuclear magnetic isotropic shieldings, the corresponding chemical shifts, and indirect spin–spin coupling constants were calculated. Several J-couplings observed in proton and carbon NMR spectra, not available before, are reported. The obtained experimental spectra, supported by theoretical calculations, favor the zwitterion form of muscimol in water. This structure differs from NH isomer, previously determined in dimethyl sulfoxide (DMSO) solution. In addition, positions of signals C3 and C5 are reversed in both solvents.     

Gauge functions and Galilean invariance of Lagrangians

A novel method to make Lagrangians Galilean invariant is developed. The method, based on null Lagrangians and their gauge functions, is used to demonstrate the Galilean invariance of the Lagrangian for Newton's law of inertia. It is suggested that this new solution of an old physics problem may have implications and potential applications to all gauge-based theories of physics.     

A differential-equation-based model of the glass ceiling in career progression

ABSTRACT

We introduce a model based on Ordinary Differential Equations to describe how two mutually exclusive groups progress through a career hierarchy, whether in a single organization, or in an entire economic sector. The intended application is to gender imbalance at the top of the academic hierarchy in European Universities; however, the model is entirely generic and may be applied in other contexts also. Previous research on gender imbalance in European universities has focused on large-scale statistical studies. Our model represents a point of departure, as it is deterministic (i.e., based on Ordinary Differential Equations). The model requires a precise definition of the progression rates for the different groups through the hierarchy; these are key parameters governing the dynamics of career progression. The progression rate for each group can be decomposed into a product: the proportion of group members at a low level in the hierarchy who compete for promotion to the next level a given year, multiplied by the in-competition success rate for the group in question. Either of these two parameters can differ across the groups under consideration; this introduces a group asymmetry into the organization’s composition. We introduce a glass-ceiling index to summarize this asymmetry succinctly. Using case studies from the literature, we demonstrate how the mathematical framework can pinpoint the proximate cause of the glass ceiling in European academia.     

Something out of nothing: a Bayesian learning computational model for the social construction of value

ABSTRACT

This article develops a formalism for the social construction of value. Using a model based on Bayesian agents, it demonstrates how “something” arises out of “nothing” via the emergence of durable value conventions and shows how the developed framework can be used to investigate socially constructed valuations under a variety of circumstances. The resulting analysis clarifies why assumptions that collectives will converge upon the “intrinsic” (i.e., non-socially originating) value of an object (e.g., market efficiency) may not hold for mixed social and non-social valuation regimes, explains the dependency of socially constructed valuations on early accidents, demonstrates the effects of confident actors on constructed values, and identifies the production of time-dependent ratcheting effects from the interaction of bubbles with value conventions.     

Influence of friction and asymmetric freeplay on the limit cycle oscillation in aeroelastic system: An extended Hénon’s technique to temporal integration

Nonlinear effects such as friction and freeplay on the control surfaces can affect aeroelastic dynamics during flight. In particular, these nonlinearities can induce limit cycle oscillations (LCO), changing the system stability, and because of this it is essential to employ computational methods to predict this type of motion during the aircraft development cycle. In this context, the present article presents a matrix notation for describing the Hénon’s method used to reduce errors when considering piecewise linear nonlinearities in the numerical integration process. In addition, a new coordinate system is used to write the aeroelastic system of equations. The proposal defines a displacement vector with generalized and physical variables to simplify the computational implementation of the Hénon’s technique. Additionally, the article discusses the influence of asymmetric freeplay and friction on the LCO of an airfoil with control surface. The results show that the extended Hénon’s technique provides more accurate LCO predictions, that friction can change the frequency and amplitude of these motions, and the asymmetry of freeplay is important to determine the LCO behavior.     

d-Xylose-based surfactants: Synthesis,characterization and molecular modeling studies

Pentose-derived surfactants were easily synthesized and fully characterized through classical analytical methods. The interfacial behaviors revealed the importance of both the length of the hydrophobic chain and the nature of the anomeric form. Finally, the spatial conformation of four xylosides was obtained by molecular modeling with software Hyperchem^® 4 using the semi-empirical method PM3, which demonstrated the role of hydrophobic interactions in the stability of the compounds.     

Functional sample path properties of subsequence's C-R increments for a Wiener process in Hlder norm

In this paper, with the aid of large deviation formulas established in strong topology of functional space generated by H¨older norm, we discuss the functional sample path properties of subsequence's C-R increments for a Wiener process in H¨older normThe obtained results,generalize the corresponding results of Chen and the classic Strassen's law of iterated logarithm for a Wiener process.     

一维线性非共轭石墨烯基(CH2)n分子链的电子输运

一维非共轭烷烃链虽不具富电子或少电子特征,但常存在于单分子器件或多肽、蛋白质等生物分子中,对电子传输产生重要影响.为理解这类物质的电子输运特征,本研究设计了一维线性非共轭(CH2)n分子结模型,并利用密度泛函理论结合非平衡态格林函数的方法,对(CH2)n(n=1-12)线性分子链与两个石墨烯电极耦合而成的分子结进行了第一性原理计算.结果表明,CH2分子链随着n值的变化,其电导值表现出明显的奇偶振荡现象,并且随着链长的增加呈指数级的衰减,这一结果与实验研究取得了很好的一致性,为理解和设计性能更加优良的单分子器件提供了重要理论依据.     

Characterization of new Pt(IV)–thiazole complexes: Analytical,spectral, molecular modeling and molecular docking studies and applications in two opposing pathways

New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl₄ salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, ¹H NMR, ¹³C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d⁶ systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO₂, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO₂ was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs.