Illustrating Chemical Concepts with Coin Flipping

Three classroom demonstrations, which involve the participation of students flipping coins, are described. The half-life of a first-order chemical reaction is illustrated by standing students sitting down when they flip a tails. Dynamic chemical equilibrium is illustrated by students standing or sitting depending on the outcome of coin-flips. In a third demonstration, the motion of gas molecules from one bulb to another is governed by the flip of a coin, showing the improbability of all the molecules gathering in just one bulb.     

Sub-ambient temperature effects on the separation of monosaccharides by high-performance anion-exchange chromatography with pulse amperometric detection: Application to marine chemistry

The effects of column temperature in the range 10–45°C using high-performance anion-exchange chromatography (HPAEC) and pulse amperometric detection are described for the determination of monosaccharides. The influence of temperature was tested with an isocratic elution of NaOH at concentrations varying from 2.5 to 20 mM and with a post-column addition of 1 M NaOH. The results showed that small changes of temperature greatly affect retention times and resolution (R_s) of monosaccharides and particularly those of the both pairs xylose–mannose and rhamnose–arabinose which cannot be simultaneously detected at usual room temperature (25°C). Our results suggest that a subambient temperature of 17°C and an eluent concentration of 19 mM are the more appropriate conditions for an acceptable separation (R_s rha/ara=1.02, R_s man/xyl=0.70) in a short analytical run time (35 min). The results showed that within the range of temperatures studied, enthalpy and entropy are invariant of temperature indicating that changes in the retention processes are mainly due to temperature than other associated changes in the system. This study demonstrated the importance of controlling temperature during HPAEC of monosaccharides, both to accomplish highly reproducible retention times and to achieve optimal separation of sugars. This method gave acceptable results for detection of marine sugars.     

The role of meningeal populations of type II innate lymphoid cells in modulating neuroinflammation in neurodegenerative diseases

Recent research into meningeal lymphatics has revealed a never-before appreciated role of type II innate lymphoid cells (ILC2s) in modulating neuroinflammation in the central nervous system (CNS). To date, the role of ILC2-mediated inflammation in the periphery has been well studied. However, the exact distribution of ILC2s in the CNS and therefore their putative role in modulating neuroinflammation in neurodegenerative diseases such as Alzheimer’s disease (AD), multiple sclerosis (MS), Parkinson’s disease (PD), and major depressive disorder (MDD) remain highly elusive. Here, we review the current evidence of ILC2-mediated modulation of neuroinflammatory cues (i.e., IL-33, IL-25, IL-5, IL-13, IL-10, TNFα, and CXCL16-CXCR6) within the CNS, highlight the distribution of ILC2s in both the periphery and CNS, and discuss some challenges associated with cell type-specific targeting that are important for therapeutics. A comprehensive understanding of the roles of ILC2s in mediating and responding to inflammatory cues may provide valuable insight into potential therapeutic strategies for many dementia-related disorders.Subject terms: Neuroimmunology, Neuroimmunology     

The 1:1 adduct of Kemp's triacid with 2‐aminopyridine

The crystal structure determination of the molecular proton‐transfer adduct of Kemp's triacid (cis‐cis‐1,3,5‐tri­methyl­cyclo­hexane‐1,3,5‐tri­carboxylic acid, KTA) with 2‐amino­pyridine (2‐APY), namely 2‐amino­pyridinium 3,5‐di­carboxy‐1,3,5‐tri­methyl­cyclo­hexane­carboxyl­ate, 2‐APY⁺·KTA^? or C₅H₇N₂⁺·C₁₂H₁₇O₆^?, has revealed a centrosymmetric hydrogen‐bonded cyclic KTA homodimer repeating unit [O?O 2.524 (4) Å] linked into a polymer structure through the pyridinium and amino groups of the 2‐APY mol­ecule [O?N 2.736 (4), 2.989 (4) and 2.999 (4) Å].     

Altitude properties and characterizations of inner product spaces

New characterizations of real inner product spaces (euclidean spaces) among metric spaces are obtained from familiar formulas expressing the altitude (height) of a triangle as a function of the lengths of its sides. Other properties related to the altitude of a triangle are also shown to result in characterizations of euclidean spaces, or euclidean and hyperbolic spaces.     

The use of MM/QM calculations of 13C and 15N chemical shifts in the conformational analysis of alkyl substituted anilines

The calculation of the ¹³C and ¹⁵N NMR chemical shifts by a combined molecular mechanics (Pcmodel 9.1/MMFF94) and ab initio (GIAO (B3LYP/DFT, 6-31 + G(d)) procedure is used to investigate the conformations of a variety of alkyl substituted anilines. The ¹³C shifts are obtained from the GIAO isotropic shielding (Ciso) with separate references for sp³ and sp² carbons (δc = δref − Ciso). The ¹⁵N shifts are obtained similarly from the GIAO isotropic shielding (Niso) with reference to the ¹⁵N chemical shift of aniline. Comparison of the observed and calculated shifts provides information on the molecular conformations. Aniline and the 2,6-dialkylanilines exist with a rapidly inverting symmetric pyramidal nitrogen atom. The 2-alkylanilines have similar conformations with the NH₂ group tilted away from the 2-alkyl substituent. The N,N-dialkylanilines show more varied conformations. N,N-dimethylaniline has a similar structure to aniline, but N-ethyl, N-methylaniline, N,N-diethylaniline, and N,N-diisopropylaniline are conformationally mobile with two rapidly interconverting conformers. In contrast, the anilines substituted at C₂ and the nitrogen atom exist as one conformer where the steric interaction between the C₂ substituent and the N substituent determines the conformation. In 2-methyl-N-methylaniline, the nitrogen atom is pyramidal as usual with the N-methyl opposite to the 2-methyl, but in 2-methyl-N,N-dimethyl aniline, the NMe₂ group is now almost orthogonal to the phenyl plane. This is also the case with 2-methyl-N,N-diethylaniline and 2,6-diisopropyl-N,N-dimethylaniline. The comparison of the observed and calculated ¹⁵N chemical shifts confirms the above findings, in particular the pyramidal conformation of aniline and the above observations with respect to the conformations of the N,N-dialkylanilines.     

Monomer sequencing and microstructural analysis on polymers of dimethyl norbornene dicarboxylate and 7‐oxanorbornene dicarboxylic derivatives employing ruthenium catalysts by ring‐opening metathesis polymerization

The physiochemical properties, comonomer sequencing, and regiospecificity of the linkages between monomeric units within homo/copolymers based on 5,6‐di‐substituted norbornene and 7‐oxanorbornene type monomers by ring‐opening metathesis polymerization are reported and correlated to their primary and secondary structural elements. In general, first‐generation Grubbs‐ I1 ruthenium catalyst generates polymers with high trans content that exhibits an extended secondary structure with exo,exo substituents, whereas second‐generation Grubbs‐ I2 catalyst produces polymers with high cis content that forms tight turns, resulting in a compact structure. Furthermore, I2 ‐produced polymers exhibit a high level of alternating cis–trans double bonds along their polymeric backbone. In stark contrast, both first‐ and second‐generation Grubbs catalysts display complete reversal in cis/trans selectivity when an oxygen atom is in position‐7 of the norbornene‐ring along with mono‐endo‐substitution in position‐5 or 6, and hence highlighting the importance of stereoelectronic complexation by the catalyst with the next incoming monomer for cis/trans selectivity. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2477–2501     

Removal of Methylene Blue from Aging Water Solutions Treated by a Submerged Arc

Low voltage, low energy submerged pulsed arcs with a pulse repetition rate of 100 Hz, energies of 2.6–192 mJ and durations of 10–40 μs, followed by aging in the dark, were used to decompose 10 mg/l methylene blue (MB) dissolved in 40 ml of water, with the addition of 0.5 % H₂O₂. Electrode pairs composed of Fe/Fe, Ti/Ti, Cu/Cu, Cu/Fe, Fe/Cu, Ti/Fe, Fe/Ti, Cu/Ti and Ti/Cu were used. MB degraded during arc treatment, and during post arc treatment aging. The aging degraded MB faster (by a factor of ~2–3) when the MB solution was subjected to arcing with dissimilar electrodes when one of them was Cu, than for arcing with other used electrode pairs. The impact of the arc treatment time and the electrode materials on the MB removal ratio (C₀–C_ta)/C₀ was determined as a function of aging time t_a, where C₀ and C_ta are the MB concentrations initially and after t_a. For a pulse duration of 10 μs and pulse energies of 2–20 mJ, the MB removal rate increased linearly with treatment time and its growth rate increased with pulse energy. The linear dependence of the MB removal rate on treatment time was violated with pulse duration of 40 μs and pulse energies of 30–200 mJ. Kinetics of the MB degradation during aging of the arc treated solution was well described by the 1st order linear rate equation.     

Structural and dielectric properties of La- and Ti-modified K0.5Na0.5NbO3 ceramics

We report the results of studies of rectifying behavior, positive magneoresistance (MR), the charge-transport mechanism and the effect of an electric field on a ZnO (n)/La_0.5Pr_0.2Sr_0.3MnO₃ (LPSMO) (p)/SrNb_0.002Ti_0.998O₃ (SNTO) (n) heterostructure comprising two p–n junctions fabricated using the pulsed laser deposition technique. The heterostructure exhibits rectifying behavior over a wide temperature and field range having hysteresis in I–V behavior (forward bias) due to the tunneling of charge carriers. It is also observed that, depending on the nature of the electric field bias to n-type ZnO and SNTO, the junction resistance becomes modified, which has been explained on the basis of spin injection in the heterostructure. The observation of unconventional positive MR at room temperature has been justified on the basis of interface effects and the reduction in barrier height obtained using fitting of the I–V data by a thermionic emission model.