Extremely fragile glass‐formers? Calorimetric and rheological determinations

We use calorimetry and rheology to investigate reports of extremely fragile polymers and the speculation that d,l ‐lactic acid should be extremely fragile. The dynamic fragilities of lactic acid, polysulfone, bisphenol‐A polycarbonate, and poly(vinyl chloride) were studied. The polymers were used as received and after a wash‐precipitation treatment. The current dynamic fragility findings are not in agreement with those reported by C. Evans, H. Deng, W. Jager, J. Torkelson, Macromolecules 2013 , 46 (15), 6091–6103 of extremely high fragilities for the mentioned polymers. We also found no sample preparation history effect on the dynamic fragility values. The calorimetric and rheological results for the d,l ‐lactic acid show dynamic fragility values that are consistent with each other and are not extremely fragile. Calorimetric measurements that use a broad range of cooling rates gave smaller dynamic fragility values than those obtained from a limited range at higher cooling rates. The importance of the results is discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1261–1272     

Alkynylgold(I) C3-Chiral Concave Complexes: Aggregation and Luminescence

Chiral gold(I) acetylide trinuclear complexes 1 – 3 based on the cyclotribenzylene platform and terminal PR₃ ligands (R=Ph, Et, and Cy, respectively), were characterized and their light emission studied. They exhibited long-lived blue phosphorescence in CHCl₃ and a weak fluorescence in the UV. In MeOH/CHCl₃ mixtures of >1:1 volume ratio, 1 and 2 exhibited a new emission band at ca. 540 nm that developed at the expense of the UV emission. DLS studies demonstrated the presence of molecular aggregates of Ø 30–80 nm. The green emission observed in MeOH-rich solvent mixtures was therefore induced by aggregation, and could originate from Au⋅⋅⋅Au interactions. The AIE spectrum of 3 was observed only in solutions containing 99 % of MeOH, and correlated with its solid state emission. The AIE profiles of the enantiomers of 1 differed from that of rac- 1 , suggesting that the latter is a true racemate.     

Computational study of the dissolution of cellulose into single chains: the role of the solvent and agitation

Cellulose - We investigate the dissolution mechanism of cellulose using molecular dynamics simulations in both water and a mixture solvent consisting of water with Na $$^+$$ , OH $$^-$$...     

Load balancing by work–stealing in quantum chemistry calculations: Application to hybrid density functional methods

Parallel implementations of quantum chemistry programs targeting supercomputers are challenging applications of dynamic load balancing algorithms. The implementation of work stealing (WS) algorithms is discussed and their usefulness is demonstrated. Evaluation of the four‐center integrals of a Cu₁₀ cluster requires 25 core‐hours overall, achieving 88% efficiency with simple WS for 2048 cores, and 97% with task presorting based on a cost estimate. Limitations of cost sorting become noticeable for larger systems. When spatial symmetry is exploited together with integral screening, bundling the original tasks yields an efficiency of 98% for Cu₇₉ in O_h symmetry on 512, 1204, and 2048 cores. The advantage of WS algorithms described in this work is not limited to the evaluation of four‐center integrals. © 2014 Wiley Periodicals, Inc.     

Solving chemical master equations by adaptive wavelet compression

Solving chemical master equations numerically on a large state space is known to be a difficult problem because the huge number of unknowns is far beyond the capacity of traditional methods. We present an adaptive method which compresses the problem very efficiently by representing the solution in a sparse wavelet basis that is updated in each step. The step-size is chosen adaptively according to estimates of the temporal and spatial approximation errors. Numerical examples demonstrate the reliability of the error estimation and show that the method can solve large problems with bimodal solution profiles.     

Pulsed DC magnetron sputtering of transparent conductive oxide layers

A comprehensive material study of different transparent conductive oxides （TCOs） is presented. The layers are deposited by pulsed direct current （DC） magnetron sputtering in an inline sputtering system. Indium tin oxide （ITO） films are studied in detail. The optimum pressure of 0.33 Pa （15Ar：202） produces a 300- nm thin film with a specific resistivity p of 2.2 × 10-6 Ωm and a visual transmittance of 81%. Alternatively, ZnO：A1 and ZnO：Ga layers with thicknesses of 200 and 250 nm are deposited with a minimum resistivity of 5.5× 10-6 and 6.8× 10-6Ωm, respectively. To compare the optical properties in the ultraviolet （UV） range, the optical spectra are modeled and the band gap is determined.     

Do complex matrices modify the sorptive properties of polydimethylsiloxane (PDMS) for non-polar organic chemicals?

The partitioning of non-polar analytes into the silicone polydimethylsiloxane (PDMS) is the basis for many analytical approaches such as solid phase microextraction (SPME), stir bar sorptive extraction (SBSE) and environmental passive sampling. Recently, the methods have been applied to increasingly complex sample matrices. The present work investigated the possible effect of complex matrices on the sorptive properties of PDMS. First, SPME fibers with a 30 μm PDMS coating were immersed in 15 different matrices, including sediment, suspensions of soil and humic substances, mayonnaise, meat, fish, olive oil and fish oil. Second, the surface of the fibers was wiped clean, and together with matrix-free control fibers, they were exposed via headspace to 7 non-polar halogenated organic chemicals in spiked olive oil. The fibers were then solvent-extracted, analyzed, and the ratios of the mean concentrations in the matrix-immersed fibers to the control fibers were determined for all matrices. These ratios ranged from 92% to 112% for the four analytes with the highest analytical precision (i.e. polychlorinated biphenyls (PCBs) 3, 28, 52 and brominated diphenyl ether (BDE) 3), and they ranged from 74% to 133% for the other three compounds (i.e. PCBs 101, 105 and γ-hexachlorocyclohexane (HCH)). We conclude that, for non-polar, hydrophobic chemicals, the sorptive properties of the PDMS were not modified by the diverse investigated media and consequently that PDMS is suited for sampling of these analytes even in highly complex matrices.