Structural verification of a tetrahydrotetrazole compound

Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C₂₅H₃₀N₄O₄, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl₃). A tentative reaction pathway for its dissociation based on ¹H NMR spectral evidence is provided.     

Finding any given 2‐factor in sparse pseudorandom graphs efficiently

Given an $n$‐vertex pseudorandom graph $G$ and an $n$‐vertex graph $H$ with maximum degree at most two, we wish to find a copy of $H$ in $G$, that is, an embedding $\phi :V\left(H\right)\to V\left(G\right)$ so that $\phi \left(u\right)\phi \left(v\right)\in E\left(G\right)$ for all $uv\in E\left(H\right)$. Particular instances of this problem include finding a triangle‐factor and finding a Hamilton cycle in $G$. Here, we provide a deterministic polynomial time algorithm that finds a given $H$ in any suitably pseudorandom graph $G$. The pseudorandom graphs we consider are $\left(p,\lambda \right)$‐bijumbled graphs of minimum degree which is a constant proportion of the average degree, that is, $\mathrm{\Omega }\left(pn\right)$. A $\left(p,\lambda \right)$‐bijumbled graph is characterised through the discrepancy property: $|e\left(A,B\right)?p|A||B||<\lambda \sqrt{|A||B|}$ for any two sets of vertices $A$ and $B$. Our condition $\lambda =O(p^{2}n/\log n)$ on bijumbledness is within a log factor from being tight and provides a positive answer to a recent question of Nenadov. We combine novel variants of the absorption‐reservoir method, a powerful tool from extremal graph theory and random graphs. Our approach builds on our previous work, incorporating the work of Nenadov, together with additional ideas and simplifications.     

Microwave‐assisted polycondensation of 4‐octylaniline with dibromoarylene

The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542     

Synthesis of diisocyanides with phenolic groups and their polymerization to helically chiral poly(quinoxaline‐2,3‐diyl)s

The development of synthetic routes which lead to five new diisocyanide monomers with one or two phenolic groups is described. Their polymerization behavior is studied with Pd‐ and Ni‐based initiators, as well as under microwave irradiation. The polymerizability is mainly dominated by steric effects as is concluded from experiments using different protecting groups. Chiroptical properties of these new polymers are studied by CD‐spectroscopy. After deprotection, helically chiral poly(quinoxalin‐2,3‐diyl)s are obtained which display a Brønsted function attached to a stereolabile biaryl axis whose configuration should be influenced by the chiral polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1320–1329     

Highly dispersed palladium nanoclusters incorporated in amino‐functionalized silica spheres for the selective hydrogenation of succinic acid to γ‐butyrolactone

Highly dispersed palladium nanoclusters incorporated on amino‐functionalized silica sphere surfaces (Pd/SiO₂‐NH₂) were fabricated by a simple one‐pot synthesis utilizing 3‐(2‐aminoethylamino)propyltrimethoxysilane (AAPTS) as coordinating agent. Uniform palladium nanoclusters with an average size of 1.1 nm can be obtained during the co‐condensation of tetraethyl orthosilicate and AAPTS owing to the strong interaction between palladium species and amino groups in AAPTS. The palladium particle size can be controlled by addition of AAPTS and plays a significant role in the catalytic performance. The Pd/SiO₂‐NH₂ catalyst exhibits high catalytic activity for succinic acid hydrogenation with 100% conversion and 94% selectivity towards γ‐butyrolactone using 1,4‐dioxane as solvent at 240°C and 60 bar for 4 h. Moreover, the Pd/SiO₂‐NH₂ catalyst is robust and readily reusable without loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

The single-polarization filter composed of gold-coated photonic crystal fiber

A single-polarization filter comprising a gold-coated photonic crystal fiber based on surface plasmon resonance is designed and investigated. The pattern matching and coupled polarization characteristics analyzed by the full-vector finite element method (FEM) and losses at 1,540 nm are achieved to 1,016.01739 dB/cm (x-pol core mode) and 33.81917 dB/cm (y-pol core mode). The crosstalk (CT) value of the 1,540 nm band is ?853.12653 dB for fiber length $L=1,000\mathrm{\mu }\text{m}$ and the bandwidth is 850 nm. The working wavelength of the filter ranges from 1,280 nm to 1,540 nm by varying the diameter of outer air holes ($d_1$), the diameter of inner air holes ($d_4$), the metal film thickness (t), as well as the liquid refractive index (n).     

Synthesis and characterization of indium and thallium immobilized on isonicotinamide‐functionalized mesoporous MCM‐41: Two novel and highly active heterogeneous catalysts for selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides

Two highly ordered isonicotinamide (INA)‐functionalized mesoporous MCM‐41 materials supporting indium and thallium (MCM‐41‐INA‐In and MCM‐41‐INA‐Tl) have been developed using a covalent grafting method. A surface functionalization method has been applied to prepare Cl‐modified mesoporous MCM‐41 material. Condensation of this Cl‐functionalized MCM‐41 with INA leads to the formation of MCM‐41‐INA. The reaction of MCM‐41‐INA with In(NO₃)₃ or Tl(NO₃)₃ leads to the formation of MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts. The resulting materials were characterized using various techniques. These MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts show excellent catalytic performance in the selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides. Finally, it is found that the anchored indium and thallium do not leach out from the surface of the mesoporous catalysts during reaction and the catalysts can be reused for seven repeat reaction runs without considerable loss of catalytic performance.     

Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156