The safer chemical design game. Gamification of green chemistry and safer chemical design concepts for high school and undergraduate students

Green chemistry can strongly attract students to chemistry. We, therefore, developed a green chemistry educational game that motivates students at the undergraduate and advanced high school levels to consider green chemistry and sustainability concerns as they design a hypothetical, chemical product. The game is intended for incorporation into any chemistry course for majors and non-majors that teaches sustainability and/or the Principles of Green Chemistry at the undergraduate level. The game is free of charge and encourages students to think like professional chemical designers and to develop a chemical product with respect to function and improved human and environmental health. This computer simulation has been assessed by educators and can be seamlessly integrated into an existing curriculum.     

A metal-complex-tolerant CuAAC 'click' protocol exemplified through the preparation of homo- and mixed-metal-coordinated [2]rotaxanes

A series of mono- and bis-metallated [2]rotaxanes has been prepared using a CuAAC 'click' protocol that is compatible with metal-coordinated building blocks and ligands; the methodology provides a general means for appending a metal ion or complex to an organic scaffold via Cu(I)-catalysed 'click' chemistry, even when the molecule contains redox-active or kinetically labile metals or vacant ligand sites.     

Long Distance Electron Transfer Across >100 nm Thick Au Nanoparticle/Polyion Films to a Surface Redox Protein

Glutathione‐decorated 5 nm gold nanoparticles (AuNPs) and oppositely charged poly(allylamine hydrochloride) (PAH) were assembled into {PAH/AuNP}_n films fabricated layer‐by‐layer (LbL) on pyrolytic graphite (PG) electrodes. These AuNP/polyion films utilized the AuNPs as electron hopping relays to achieve direct electron transfer between underlying electrodes and redox proteins on the outer film surface across unprecedented distances >100 nm for the first time. As film thickness increased, voltammetric peak currents for surface myoglobin (Mb) on these films decreased but the electron transfer rate was relatively constant, consistent with a AuNP‐mediated electron hopping mechanism.     

Mesoporous carbon amperometric glucose sensors using inexpensive,commercial methacrylate-based binders

Two ordered, soft-templated mesoporous carbon powders with cubic and hexagonal framework structure and four different commercial, low cost methacrylate-based polymer binders with widely varying physical properties are investigated as screen printed electrodes for glucose sensors using glucose oxidase and ferricyanide as the mediator. Both the chemistry and concentration of the binder in the electrode formulation can significantly impact the performance. Poly(hydroxybutyl methacrylate) as the binder provides hydrophilicity to enable transport of species in the aqueous phase to the carbon surface, but yet is sufficiently hydrophobic to provide mechanical robustness to the sensor. The current from the mesoporous carbon electrodes can be more than an order of magnitude greater than for a commercial printed carbon electrode (Zensor) with improved sensitivity for model glucose solutions. Even when applying these sensors to rabbit whole blood, the performance of these glucose sensors compares favorably to a standard commercial glucose meter with the lower detection limit of the mesoporous electrode being approximately 20 mg dL⁻¹ despite the lack of a separation membrane to prevent non-specific events; these results suggest that the small pore sizes and high surface areas associated with ordered mesoporous carbons may effectively decrease some non-specific inferences for electrochemical sensing.     

Built to order: molecular tinkertoys from the [Re(6)(mu(3)-Se)(8)](2+) clusters

Ligand substitution of [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CH(3)CN)](SbF(6))(2) (1) with pyridyl-based ligands, 2,4,6-tri-4-pyridyl-1,3,5-triazine (L1) and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (L2), produced respectively the star-shaped tricluster (T1) and tetracluster (T2) arrays, wherein three (T1) and four (T2) units of the [Re(6)(mu(3)-Se)(8)](2+) core-containing clusters are interconnected by the corresponding bridging ligands. These novel supramolecular assemblies were characterized by a combination of NMR ((1)H and (31)P) spectroscopy, ESI-MS, and microanalysis. The molecular and solid-state structures of T1 have also been established by single-crystal X-ray diffraction.     

Two Equivalent Reduction of Copper(I) Complexes; Evidence of an Anionic Copper Species

Reactive copper solutions have been prepared by a cold temperature, two equivalent lithium naphthalenide reduction of copper(I) complexes. One equivalent of organic halides react with one equivalent of the anionic copper to yield organocopper reagents.     

Impact of chain architecture (branching) on the thermal and mechanical behavior of polystyrene thin films

The modulus and glass transition temperature (T_g) of ultrathin films of polystyrene (PS) with different branching architectures are examined via surface wrinkling and the discontinuity in the thermal expansion as determined from spectroscopic ellipsometry, respectively. Branching of the PS is systematically varied using multifunctional monomers to create comb, centipede, and star architectures with similar molecular masses. The bulk‐like (thick film) T_g for these polymers is 103 ± 2 °C and independent of branching and all films thinner than 40 nm exhibit reductions in T_g. There are subtle differences between the architectures with reductions in T_g for linear (25 °C), centipede (40 °C), comb (9 °C), and 4 armed star (9 °C) PS for ≈ 5 nm films. Interestingly, the room temperature modulus of the thick films is dependent upon the chain architecture with the star and comb polymers being the most compliant (≈2 GPa) whereas the centipede PS is most rigid (≈4 GPa). The comb PS exhibits no thickness dependence in moduli, whereas all other PS architectures examined show a decrease in modulus as the film thickness is decreased below ～40 nm. We hypothesize that the chain conformation leads to the apparent susceptibility of the polymer to reductions in moduli in thin films. These results provide insight into potential origins for thickness dependent properties of polymer thin films. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Comment on the paper: H.-E. Hwang, P. Han, Theoretical analysis for surface tilt and translation detection based on speckle photography in the Fresnel domain, Opt. Commun. 282 (2009) 351-354

In a recent paper [H.-E. Hwang, P. Han, Opt. Commun. 282 (2009) 351] a speckle based metrology system is proposed which it is claimed provides significant advantages over existing systems. In this paper, we show that the discussion presented in [H.-E. Hwang, P. Han, Opt. Commun. 282 (2009) 351] is deficient, and that several of the statements made are incorrect and/or misleading.     

Convergence of zeta functions of graphs

The -zeta function of an infinite graph (defined previously in a ball around zero) has an analytic extension. For a tower of finite graphs covered by , the normalized zeta functions of the finite graphs converge to the -zeta function of .