Efficient implementation of the analytic second derivatives of Hartree–Fock and hybrid DFT energies: a detailed analysis of different approximations

In this paper, various implementations of the analytic Hartree–Fock and hybrid density functional energy second derivatives are studied. An approximation-free four-centre implementation is presented, and its accuracy is rigorously analysed in terms of self-consistent field (SCF), coupled-perturbed SCF (CP-SCF) convergence and prescreening criteria. The CP-SCF residual norm convergence threshold turns out to be the most important of these. Final choices of convergence thresholds are made such that an accuracy of the vibrational frequencies of better than 5 cm^?1 compared to the numerical noise-free results is obtained, even for the highly sensitive low frequencies (<100–200 cm^?1). The effects of the choice of numerical grid for density functional exchange–correlation integrations are studied and various weight derivative schemes are analysed in detail. In the second step of the work, approximations are introduced in order to speed up the computation without compromising its accuracy. To this end, the accuracy and efficiency of the resolution of identity approximation for the Coulomb terms and the semi-numerical chain of spheres approximation to the exchange terms are carefully analysed. It is shown that the largest performance improvements are realised if either Hartree–Fock exchange is absent (pure density functionals) and otherwise, if the exchange terms in the CP-SCF step of the calculation are approximated by the COSX method in conjunction with a small integration grid. Default values for all the involved truncation parameters are suggested. For vancomycine (176 atoms and 3593 basis functions), the RIJCOSX Hessian calculation with the B3LYP functional and the def2-TZVP basis set takes ～3 days using 16 Intel® Xeon® 2.60GHz processors with the COSX algorithm having a net parallelisation scaling of 11.9 which is at least ～20 times faster than the calculation without the RIJCOSX approximation.     

Polydipropylsiloxane Single Crystals

Polydipropylsiloxane single crystals, grown from a dilute n-butylacetate solution, were characterized by electron microscopy and by selected-area electron-beam diffraction techniques. The electron diffraction study shows that the growth face was parallel to the (100) plane. Fracture of single crystals parallel to the fold plane takes place during the electron diffraction examination to give ribbon like lamellae about 300 A wide and 80 A thick. Fracture normal to the fold plane was also observed.     

Quality assurance in immunoassay performance—comparison of different enzyme immunoassays for the determination of caffeine in consumer products

Enzyme immunoassays with optical detection are amongst the most widely used bioanalytical tools. We defined seven parameters for the quality assessment of immunoassays that were addressed in a systematic study of direct and indirect immunoassays, using the enzymes horseradish peroxidase (HRP) and alkaline phosphatase (AP), the chromogenic substrates 3,3′,5,5′-tetramethylbenzidine (TMB) and para-nitrophenyl phosphate, and the fluorescent substrates 3-(4-hydroxyphenyl)propionic acid and 4-methylumbelliferyl phosphate. The same monoclonal antibody against caffeine was used throughout the study. The four quality parameters regarding the standard curve were the test midpoint (sensitivity), the measurement range, the relative dynamic range of the signal, and the goodness of fit of the adjusted four-parameter logistic function. All HRP immunoassays showed a higher sensitivity compared to the AP assays. On the basis of all four criteria, it was established that the direct assay format is superior to the indirect format, the immunoassay using HRP TMB fulfilling all requirements best. In a second step, caffeine concentrations in 24 beverage and cosmetics samples were determined and three more quality parameters were assessed with this application. The direct HRP TMB assay showed one of the best intra- and inter-plate precisions and the best accuracy, defined by the correlation of results with those from the chosen reference method liquid chromatography tandem mass spectrometry (LC-MS/MS). Considering all criteria, HRP TMB seems to be the enzyme substrate system of choice preferably used in the direct assay format.

Molecule-based kinetic modeling by Monte Carlo methods for heavy petroleum conversion

A methodology for kinetic modeling of conversion processes is presented.The proposed approach allows to overcome the lack of molecular detail of the petroleum fractions and to simulate the reactions of the process by means of a two-step procedure.In the first step,a synthetic mixture of molecules representing the feedstock is generated via a molecular reconstruction method,termed SR-REM molecular reconstruction.In the second step,a kinetic Monte Carlo method,termed stochastic simulation algorithm(SSA),is used to simulate the effect of the conversion reactions on the mixture of molecules.The resulting methodology is applied to the Athabasca vacuum residue hydrocracking.An adequate molecular representation of the vacuum residue is obtained using the SR-REM algorithm.The reaction simulations present a good agreement with the laboratory data for Athabasca vacuum residue conversion.In addition,the proposed methodology provides the molecular detail of the vacuum residue conversion throughout the reactions simulations.     

Bent‐core mesogens based on semi‐flexible dicyclohexylmethane spacers

New, bent‐core mesogens are described in which the core of the molecule is a semiflexible, di(4‐aminocyclohexyl)methane spacer. The compounds show nematic, columnar nematic and columnar phases as shown by a combination of X‐ray diffraction and optical microscopy. The potential of these new mesogens as biaxial nematic candidates is considered.     

Improved Synthesis of Cyclic Tertiary Allylic Alcohols by Asymmetric 1,2‐Addition of AlMe3 to Enones

The development of an improved protocol for the enantioselective Rh^I/binap‐catalysed 1,2‐addition of AlMe₃ to cyclic enones is reported. ³¹P NMR analysis of the reaction revealed that the catalyst in its resting state is a chloride‐bridged dimer. This insight led to the use of AgBF₄ as an additive for in situ activation of the dimeric precatalyst. Thus, the catalyst loading can now be reduced to only 1 mol % with respect to rhodium. Various 5–7‐membered cyclic enones can be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (?)‐frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component “wine lactone”.     

Common Trends and Differences in Antioxidant Activity Analysis of Phenolic Substances Using Single Electron Transfer Based Assays

Numerous assays were developed to measure the antioxidant activity, but each has limitations and the results obtained by different methods are not always comparable. Popular examples are the DPPH and ABTS assay. Our aim was to study similarities and differences of these two assay regarding the measured antioxidant potentials of 24 phenolic compounds using the same measurement and evaluation methods. This should allow conclusions to be drawn as to whether one of the assays is more suitable for measuring specific subgroups like phenolic acids, flavonols, flavanones, dihydrochalcones or flavanols. The assays showed common trends for the mean values of most of the subgroups. Some dihydrochalcones and flavanones did not react with the DPPH radical in contrast to the ABTS radical, leading to significant differences. Therefore, to determine the antioxidant potential of dihydrochalcone or flavanone-rich extracts, the ABTS assay should be preferred. We found that the results of the flavonoids in the DPPH assay were dependent on the Bors criteria, whereas the structure–activity relationship in the ABTS assay was not clear. For the phenolic acids, the results in the ABTS assay were only high for pyrogallol structures, while the DPPH assay was mainly determined by the number of OH groups.