The reaction of homophthalic acid and some aza analogues with vilsmeier reagent: a reinvestigation

Homophthalic acid and its pyrido and 8‐methylquinolino analogues with dimethylformamide/phosphoryl chloride at 0 ° give the appropriate 4‐(dimethylaminomethylene)isochroman‐1,3‐dione ( 2a, 2b, 2c , respectively). Under the literature conditions for conversion of 2a to 2‐methyl‐1‐oxo‐1,2‐dihydroisoquinoline‐4‐carboxylic acid ( 3a ), the aza analogues give instead 7‐hydroxy‐5‐oxo‐5H‐pyrano[4,3‐b]pyridine‐8‐carbox‐aldehyde ( 5b ) and 3‐hydroxy‐6‐methyl‐1‐oxo‐1H‐pyrano[4,3‐b]quinoline‐4‐carboxaldehyde ( 5c ), respectively. Modified conditions were required to isolate analogues 3b and 3c . Further, while reaction of 2a with hydrogen chloride in methanol gave the known change to methyl 1‐oxo‐1H‐isochromene‐4‐carboxylate ( 4 ), 2b and 2c gave only products of oxa‐ring cleavage. Methyl 2‐(cis‐2‐hydroxyvinyl)‐8‐methylquinoline‐3‐carboxylate ( 8 ) was the main product from 2c , while a novel quinolizinium species ( 11 ) was formed in good yield from 2b.     

Studies in hydrogen bonding: simulation of the crystalline solids of ice, ammonia, and ammonia hydrate

The crystal structures of ice, ammonia and ammonia hydrate have been simulated with rigid molecules using the interatomic potential function EPEN/2 and the computer program WMIN. Structural parameters were adjusted to give structures with minimum energy. The hydrogen bonding in the simulated structures is compared with that in the experimental structures.     

Amino(oligo)thiophene-based environmentally sensitive biomembrane chromophores

There is a growing need for cellular imaging with fluorescent probes that emit at longer wavelengths to minimize the effects of absorption, autofluorescence, and scattering from biological tissue. In this paper a series of new environmentally sensitive hemicyanine dyes featuring amino(oligo)thiophene donors have been synthesized via aldol condensation between a 4-methylpyridinium salt and various amino(oligo)thiophene carboxaldehydes, which were, in turn, obtained from amination of bromo(oligo)thiophene carboxaldehyde. Side chains on these fluorophores impart a strong affinity for biological membranes. Compared with benzene analogues, these thiophene fluorophores show significant red shift in the absorption and emission spectra, offering compact red and near-infrared emitting fluorophores. More importantly, both the fluorescence quantum yields and the emission peaks are very sensitive to various environmental factors such as solvent polarity or viscosity, membrane potential, and membrane composition. These chromophores also exhibit strong nonlinear optical properties, including two-photon fluorescence and second harmonic generation, which are themselves environmentally sensitive. The combination of long wavelength fluorescence and nonlinear optical properties make these chromophores very suitable for applications that require sensing or imaging deep inside tissues.     

Performance comparison using the GUESS mixture to evaluate counter-current chromatography instruments

Comparing the performance of different counter-current chromatography (CCC) J-type centrifuges has and will always be difficult. This is due to the number of variables such as speed of rotation, swung radius, β-value, column bore, column length that can be chosen during the design of an instrument. This situation is further complicated by the implication that some of these variables are intrinsically linked, such that if one is changed another or others can also change. The chromatographer has no influence on these hardware parameters once the instrument designer has chosen them. However, the chromatographer wants a CCC column that retains the most liquid stationary phase in order to achieve the best separation of the components in a mixture. What matters most is column performance in terms of: sample loading per injection, speed of separation, purity of target and yield of target. The instrument that has the best performance in all these areas is called a “high-performance” CCC system. This paper demonstrates to the modern chromatographer that a “high-performance” CCC instrument has shorter, lower volume columns that are rotated faster to provide quicker separations, even with the same sample loading.     

Solvothermal depolymerization and recrystallization of imine-linked two-dimensional covalent organic frameworks

Mechanistic understanding into the formation and growth of imine-linked two-dimensional (2D) covalent organic frameworks (COFs) is needed to improve their materials quality and access larger crystallite sizes, both of which limit the promise of 2D COFs and 2D polymerization techniques. Here we report a previously unknown temperature-dependent depolymerization of colloidal 2D imine-linked COFs, which offers a new means to improve their crystallinity. 2D COF colloids form at room temperature but then depolymerize when their reaction mixtures are heated to 90 °C. As the solutions are cooled back to room temperature, the 2D COFs repolymerize and crystallize with improved crystallinity and porosity, as characterized by X-ray diffraction, infrared spectroscopy and N₂ porosimetry. The evolution of COF crystallinity during the solvothermal depolymerization and repolymerization processes was characterized by in situ wide angle X-ray scattering, and the concentrations of free COF monomers as a function of temperature were quantified by variable temperature ¹H NMR spectroscopy. The ability of a 2D COF to depolymerize under these conditions depends on both the identity of the COF and its initial materials quality. For one network formed at room temperature (TAPB-PDA COF), a first depolymerization process is nearly complete, and the repolymerization yields materials with dramatically enhanced crystallinity and surface area. Already recrystallized materials partially depolymerize upon heating their reaction mixtures a second time. A related 2D COF (TAPB-DMTA COF) forms initially with improved crystallinity compared to TAPB-PDA COF and then partially depolymerizes upon heating. These results suggest that both high materials quality and network-dependent properties, such as interlayer interaction strength, influence the extent to which 2D COFs resist depolymerization. These findings offer a new means to recrystallize or solvent anneal 2D COFs and may ultimately inform crystallization conditions for obtaining large-area imine-linked two-dimensional polymers from solution.

Conditions for which imine-linked 2D COF polymerizations are temperature-sensitive are identified that enable a dissolution/repolymerization process akin to molecular recrystallization.     

Ab initio excited-state dynamics of the photoactive yellow protein chromophore

The photoisomerization mechanism of the neutral form of the photoactive yellow protein (PYP) chromophore is investigated using ab initio quantum chemistry and first-principles nonadiabatic molecular dynamics (ab initio multiple spawning or AIMS). We identify the nature of the two lowest-lying excited states, characterize the short-time behavior of molecules excited directly to S2, and explain the origin of the experimentally observed wavelength-dependent photoisomerization quantum yield.     

Novel siloxane polymers as polymer electrolytes for high energy density lithium batteries

A variety of disubstituted (double-comb) polysiloxane polymers have been prepared containing linear, branched, and cyclic oligoethyleneoxide units, –(OCH₂CH₂)_n–, in the side chains and as part of the siloxane backbone. Copolymers, using mixtures of linear ethylene oxide side chains, were also synthesized. These polymers were doped with LiN(SO₂CF₃)₂ (LiTFSI, 1) and conductivities of the polymer-salt complexes were determined as a function of temperature and doping level. The maximum conductivity of these polymers at 25 ° C was 2.99 ×10^–4, for a copolymer containing equimolar amounts of side chains with n = 5 and 6.     

A phloroglucinol derivative with a new carbon skeleton from Hypericum perforatum (Guttiferae)

Examination of the aerial parts of a Chinese herbal medicine yielded a novel metabolite, perforatumone 1, which is characterized by its unique carbon skeleton. Its structure was determined by detailed spectroscopic analysis.     

Thermodynamic clarification of the curious ferric/potassium ion exchange accompanying the electrochromic redox reactions of prussian blue, iron(III) hexacyanoferrate(II)

The recent Glasser-Jenkins method for lattice-energy prediction, applied to an examination of the solid-state thermodynamics of the cation exchanges that occur in electrochromic reactions of Prussian Blue, provides incisive thermodynamic clarification of an ill-understood ion exchange that accompanies particularly the early electrochromic cycles. A volume of 0.246 +/- 0.017 nm(3) formula unit(-1) for the ferrocyanide ion, Fe(II)[(CN)(6)],(4-) is first established and then used, together with other formula unit-volume data, to evaluate the changes of standard enthalpy, entropy, and Gibbs energy in those ion-exchange reactions. The results impressively show by how much the exchange of interstitial Fe(3+) ions by alkali metal ions, usually exemplified by K+, is thermodynamically favored.