Localized hydrogels based on cellulose nanofibers and wood pulp for rapid removal of methylene blue

Access to clean water has become increasingly difficult, motivating the need for materials that can efficiently remove pollutants. Hydrogels have been explored for remediation, but they often require long times to reach high levels of adsorption. To overcome this limitation, we developed a rapid, locally formed hydrogel that adsorbs dye during gelation. These hydrogels are derived from cellulose—a renewable, nontoxic, and biodegradable resource. More specifically, we found that sulfated cellulose nanofibers or sulfated wood pulps, when mixed with a water-soluble, cationic cellulose derivative, efficiently remove methylene blue (a cationic dye) within seconds. The maximum adsorption capacity was found to be 340 ± 40 mg methylene blue/g cellulose. As such, these localized hydrogels (and structural analogues) may be useful for remediating other pollutants.     

Boron–Nitrogen-Doped Nanographenes: A Synthetic Tale from Borazine Precursors

In this work, a comprehensive account of the authors’ synthetic efforts to prepare borazino-doped hexabenzocoronenes by using the Friedel–Crafts-type electrophilic aromatic substitution is reported. Hexafluoro-functionalized aryl borazines, bearing an ortho fluoride leaving group on each of the N- and B-aryl rings, was shown to lead to cascade-type electrophilic aromatic substitution events in the stepwise C−C bond formation, giving higher yields of borazinocoronenes than those obtained with borazine precursors bearing fluoride leaving groups at the ortho positions of the B-aryl substituents. By using this pathway, an unprecedented boroxadizine-doped PAH featuring a gulf-type periphery could be isolated, and its structure proven by single-crystal X-ray diffraction analysis. Mechanistic studies on the stepwise Friedel–Crafts-type cyclization suggest that the mechanism of the planarization reaction proceeds through extension of the π system. To appraise the doping effect of the boroxadizine unit on the optoelectronic properties of topology-equivalent molecular graphenes, the all-carbon and pyrylium PAH analogues, all featuring a gulf-type periphery, were also prepared. As already shown for the borazino-doped hexabenzocoronene, the replacement of the central benzene ring by its B₃N₂O congener widens the HOMO–LUMO gap and dramatically enhances the fluorescence quantum yield.     

Redox Stability Controls the Cellular Uptake and Activity of Ruthenium-Based Inhibitors of the Mitochondrial Calcium Uniporter (MCU)

The mitochondrial calcium uniporter (MCU) is the ion channel that mediates Ca²⁺ uptake in mitochondria. Inhibitors of the MCU are valuable as potential therapeutic agents and tools to study mitochondrial Ca²⁺. The best-known inhibitor of the MCU is the ruthenium compound Ru360. Although this compound is effective in permeabilized cells, it does not work in intact biological systems. We have recently reported the synthesis and characterization of Ru265, a complex that selectively inhibits the MCU in intact cells. Here, the physical and biological properties of Ru265 and Ru360 are described in detail. Using atomic absorption spectroscopy and X-ray fluorescence imaging, we show that Ru265 is transported by organic cation transporter 3 (OCT3) and taken up more effectively than Ru360. As an explanation for the poor cell uptake of Ru360, we show that Ru360 is deactivated by biological reductants. These data highlight how structural modifications in metal complexes can have profound effects on their biological activities.     

Thermal Elimination of Ethylene from Cyclobutyl Groups Characterized by X-ray Crystallography in a Metal–Organic Framework Matrix

Methods to synthesize and characterize aromatic molecules with vinyl substituents are sought after yet limited in the literature. Here, we introduce cyclobutyl groups into a metal–organic framework (MOF) matrix that are poised to produce ethylene upon heating. The expulsion of ethylene produces vinyl groups on an aromatic core, which are isolated by the crystalline matrix of the framework. This enables full characterization of the thermolysis by single-crystal X-ray diffraction. Further, we modify the vinyl groups by a bromine addition reaction. Importantly, the two transformations happen in a single-crystal-to-single-crystal manner without changing the overall network structure of the parent framework. New insights into the structural and synthetic chemistry of this important class of compound are generated. Installing reactive vinyl tags in materials by the high temperature thermolysis of cyclobutyl groups is a powerful strategy for altering their physicochemical characteristics.     

Molecular salts with diquat-based electron acceptors for nonlinear optics

We have used several techniques, including Stark spectroscopy and MO calculations, to investigate the optical and electronic properties of two new dipolar chromophoric cations containing diquat-based electron acceptor groups. Both the Stark data and the calculated parameters show that the strong electron-accepting properties of a diquat unit lead to static first hyperpolarizabilities beta0 which are considerably larger than those of a related stilbazolium chromophore. In addition, one compound has a strongly 2D quadratic NLO response, providing a very rare example of a charged molecule displaying such behavior.     

Long-term phosphorus effects on evolving physicochemical properties of iron and aluminum hydroxides

Iron (Fe) and aluminum (Al) hydroxides are highly reactive components in environmental processes, such as contaminant fate and transport. Phosphorus (P) sorption by these components can decrease environmental problems associated with excess accumulation of P in soils. The long-term stability of P sorbed by Fe/Al hydroxides is of major concern. Synthetic Fe and Al hydroxides coprecipitated with P (1:1 metal:P molar ratio) were incubated at 70 degrees C for 24 months to simulate natural long-term weathering processes that could influence the stability of sorbed P. Heat incubation (70 degrees C) of the untreated (no P) Al hydroxides resulted in drastic decreases (within the first month of incubation) in oxalate-Al extractability, specific surface area (SSA), and micropore volume with time. These changes were consistent with the formation of pseudoboehmite. Untreated Fe hydroxides showed no formation of crystalline components following heating (70 degrees C) for 24 months. Much smaller changes in oxalate-Al, P extractability, and SSA values were observed in the P-treated Al particles when compared with the untreated. Phosphorus treatment of both Fe and Al hydroxides stabilized the particle surfaces and prevented structural arrangements toward a long-range ordered phase. Slight reduction in SSA of the P-treated particles was related to dehydration phenomena during heating at 70 degrees C. Monitoring of physicochemical properties of the solids after heating at 70 degrees C for 2 years showed that sorbed P may be stable in the long-term. Understanding long term physicochemical properties may help engineers to optimize the Fe/Al hydroxides performance in several environmental/industrial applications.     

Nitrogen balance and delta15N: why you're not what you eat during nutritional stress

While past experiments on animals, birds, fish, and insects have shown changes in stable isotope ratios due to nutritional stress, there has been little research on this topic in humans. To address this issue, a small pilot study was conducted. Hair samples from eight pregnant women who experienced nutritional stress associated with the nausea and vomiting of morning sickness (hyperemesis gravidarum) were measured for carbon (delta13C) and nitrogen (delta15N) stable isotope ratios. The delta13C results showed no change during morning sickness or pregnancy when compared with pre-pregnancy values. In contrast, the delta15N values generally increased during periods of weight loss and/or restricted weight gain associated with morning sickness. With weight gain and recovery from nutritional stress, the hair delta15N values displayed a decreasing trend over the course of gestation towards birth. This study illustrates how delta15N values are not only affected by diet, but also by the nitrogen balance of an individual. Potential applications of this research include the development of diagnostic techniques for tracking eating disorders, disease states, and nitrogen balance in archaeological, medical, and forensic cases.     

Pyrazolo[1,5-a]pyridines as p38 kinase inhibitors

[reaction: see text] A convergent synthesis of substituted pyrazolo[1,5-a]pyridines has been achieved either via a regioselective [3 + 2] cycloaddition of N-aminopyridines with alkynes or by thermal cyclization of disubstituted azirines. Subsequent palladium-catalyzed introduction of pyridines or de novo synthesis of pyrimidines affords inhibitors of p38 kinase.     

Glauberman-Watanabe corresponding -blocks of finite groups with normal defect groups are Morita equivalent

Let be a finite group and let be a solvable finite group that acts on such that the orders of and are relatively prime. Let be a -block of with normal defect group such that stabilizes and . Then there is a Morita equivalence between the block and its Watanabe correspondent block of given by a bimodule with vertex and trivial source that on the character level induces the Glauberman correspondence (and which is an isotypy by a theorem of Watanabe).

     

Observation of a resonance in Chi(1835) in J/psi --> gammapi+ pi- eta-

The decay channel J/psi --> gamma(pi)(+)pi(-)eta is analyzed using a sample of 5.8 x 10(7) J/psi events collected with the BESII detector. A resonance, the Chi(1835), is observed in the pi(+)pi(-)eta invariant-mass spectrum with a statistical significance of 7.7 sigma. A fit with a Breit-Wigner function yields a mass M = 1833.7 +/- 6.1(stat) +/- 2.7(syst) MeV/c(2), a width Tau = 67.7 +/- 20.3(stat) +/- 7.7(syst) MeV/c(2), and a product branching fraction B(J/psi --> gammaChi) . B(Chi --> pi(+)pi(-)eta) = [2.2 +/- 0.4(stat) +/- 0.4(syst)] x 10(-4). The mass and width of the Chi(1835) are not compatible with any known meson resonance. Its properties are consistent with expectations for the state that produces the strong pp mass threshold enhancement observed in the J/psi --> gammapp process at BESII.