Group 3 metal complexes of radical-anionic 2,2'-bipyridyl ligands

A new method for generating group 3 metal complexes containing radical-anionic 2,2'-bipyridyl (bipy) ligands is described that relies on hydrogen-atom abstraction from dearomatized biheterocyclic complexes. This method does not involve electron transfer to neutral 2,2'-bipyridyl or salt metathesis between the lithium salt of the 2,2'-bipyridyl radical anion and group 3 metal halides. The new metal complexes were characterized by single-crystal X-ray diffraction, electron paramagnetic resonance, and absorption spectroscopy. Density functional theory (DFT) calculations were used to probe the electronic structure of these compounds. All these methods support the radical-anionic character of bipy in all bipy compounds presented.     

Synthetic and structural studies on some 1,3-diselena- and 1,3-dithia-[3]ferrocenophanes of germanium and tin. crystal and molecular structure of 1,3-diselena-2,2- dichlorogermyl-[3]ferrocenophane

A series of [3]ferrocenophanes of general formula Fe(C₅H₄X)₂YCl₂ and the spiro compounds [Fe(C₅H₄X)₂]₂Ge (X = S, Se; Y = Ge, Sn) have been prepared by the reaction of ferrocene 1,1′-dithiol and ferrocene 1,1′-diselenol with tetrahalides of germanium and tin. Spectroscopic properties of the compounds are reported. In solution, the compounds are fluxional by a bridge reversal process. The crystal structure of 1,3-diselena-2,2-dichlorogermyl-[3]ferrocenophane at 163 K. has been determined by X-ray diffraction methods. At that temperature, crystals have space group P2₁/n with a 6.222(3), b 16.156(13), c 12.968(4) Å, β 97.53(1)° and Z = 4. Least-squares refinement gave R = 0.033 for 2834 unique significant reflections whose intensities were measured by counter diffractometry. The two SeGe bond lengths are 2.323 and 2.325(1) Å, with GeCl 2.148 and 2.161(1) Å. The SeGeSe bond angle is 118.2(1)°, ClGeCl 104.7(1)°, and SeGeCl angles range from 106.2 to 109.8(1)°. The SeC bond lengths are 1.901 and 1.904(5) Å, with CSeGe angles of 95.8 and 96.5(2)°. The cyclopentadienyl rings are in an eclipsed conformation with a mean twist angle of 2.7°, and are inclined to one another at 6.1°. The Se atoms are displaced from the ring planes by 0.17 and 0.20 Å yielding a non-bonded intramolecular Se…Se contact of 3.99 Å.     

Hybrid protein-lipid patterns from aluminum templates

An aqueous aluminum liftoff process suitable for fabrication of hybrid patterns of protein and supported lipid membrane on silica surfaces is described. Patterned aluminum thin films, which can be produced by conventional optical or electron beam lithography, are employed as sacrificial protecting layers to define the geometry of the protein-lipid patterns. The aluminum is lifted off in a mildly basic aqueous solution, which preserves the integrity of bound protein layers. The newly exposed substrate can then be filled with supported membrane by exposure to an aqueous vesicle suspension. The final substrate consists of patterned protein and lipid membranes with spatial resolution determined by aluminum patterns, down to 200 nm line widths in this case. Inorganic surfaces were characterized by atomic force microscopy and X-ray photoelectron spectroscopy while supported bilayers and protein patterns were characterized by epifluorescence microscopy.     

Separation-based approach to study dissociation kinetics of noncovalent DNA-multiple protein complexes

Noncovalent binding of DNA with multiple proteins is pivotal to many regulatory cellular processes. Due to the lack of experimental approaches, the kinetics of assembly and disassembly of DNA-multiple proteins complexes have never been studied. Here, we report on a first method capable of measuring disassembly kinetics of such complexes. The method is based on continuous spatial separation of different complexes. The kinetics of multiple complex dissociation processes are also spatially separated, which in turn facilitates finding their rate constants. Our separation-based approach was compared with a conventional no-separation approach by using computer simulation of dissociation kinetics. It proved to be much more accurate than the no-separation approach and to be a powerful tool for testing hypothetical mechanisms of the disassembly of DNA-multiple proteins complexes. An experimental implementation of the separation-based approach was finally demonstrated by using capillary electrophoresis as a separation method. The interaction between an 80 nucleotide long single-stranded DNA and single-stranded DNA binding protein was studied. DNA-protein complexes with one and two proteins were observed, and rate constants of their dissociation were determined. We foresee that a separation approach will be also developed to study the kinetics of the formation of DNA-multiple protein complexes.     

PEG- and peptide-grafted aliphatic polyesters by click chemistry

Novel aliphatic polyesters with pendent acetylene groups were prepared by controlled ring-opening polymerization and subsequently used for grafting poly(ethylene glycol) and oligopeptide moieties by the Cu(I)-catalyzed addition of azides and alkynes, a type of "click" chemistry. These aliphatic polyesters possess an acetylene graft density that can be tailored by ring-opening copolymerization of alpha-propargyl-delta-valerolactone (1) with epsilon-caprolactone. Since the mild conditions associated with the click reaction are shown to be compatible with the polyester backbone, this method is a generally useful means for grafting numerous types of functionality onto aliphatic polyesters. The amphiphilic graft polyesters prepared in this study are shown to be biocompatible by in vitro cytotoxicity evaluation, suggesting their suitability for a range of biomaterial applications.     

Membrane Proteins Have Distinct Fast Internal Motion and Residual Conformational Entropy

The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling.     

Iridium(III) Complexes Bearing Pyrene‐Functionalized 1,10‐Phenanthroline Ligands as Highly Efficient Sensitizers for Triplet–Triplet Annihilation Upconversion

“Chemistry‐on‐the‐complex” synthetic methods have allowed the selective addition of 1‐ethynylpyrene appendages to the 3‐, 5‐, 3,8‐ and 5,6‐positions of Ir^III‐coordinated 1,10‐phenanthroline via Sonogashira cross‐coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8‐substituted Ir‐3 : λ_abs=481 nm, ?=52 400 m ^?1 cm^?1) and long‐lived triplet excited states (e.g. 5‐substituted Ir‐2 : τ_T=367.7 μs) were observed for the complexes in deaerated CH₂Cl₂. On testing the series as triplet sensitizers for triplet–triplet annihilation upconversion, those Ir^III complexes bearing pyrenyl appendages at the 3‐ and 3,8‐positions ( Ir‐1 , Ir‐3 ) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively).     

Improving neutron activation analysis accuracy for the measurement of gold in the characterization of heterogeneous catalysts using a TRIGA reactor

To measure the gold content of a catalyst accurately, neutron activation analysis (NAA) is one of the methods of choice. NAA is preferred for such heterogeneous catalysts because: (1) it requires minimal sample preparation; (2) NAA provides consistent and accurate results; and (3) in most cases results are obtained much quicker than competing methods. NAA is also used as a referee for the other elemental techniques when results do not fall within expected statistical uncertainties. However, at very high gold concentrations, applying NAA to determine the gold in a heterogeneous catalyst is more challenging than a routine NAA procedure. On the one hand, the neutron absorption cross section for gold is very high, resulting in significant self-shielding related errors. On the other hand, gold exhibits low energy resonance neutron absorptions. In this application the self-shielding minimization effort was handled more rigorously than the classic suppression of neutron flux within a specimen. This non-routine approach was used because: (1) for most applications, high accuracy, <3 % relative, is desired, (2) the low energy resonances of gold make its neutron reaction rate complex and (3) the TRIGA reactor flux profile used in this study contains both thermal and significant epithermal neutron fluxes. Accuracy and precision, using this new approach, are expected to improve from 15 % to better than 3 % relative uncertainty. This has been accomplished through a rigorous assessment of the observed effects of low energy resonance on the neutron flux spectral shape within the sample and designing an experiment to minimize the effects.     

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.