Improved SEC-FTIR method for the characterization of multimodal high-density polyethylenes

A size-exclusion chromatography-Fourier transform infrared spectroscopy (SEC-FTIR) method for the analysis of high-density polyethylene copolymers was developed, providing superior resolution for the determination of short-chain branching as a function of time and improved repeatability by hardware adaptation and processing optimization. SEC-FTIR for characterization of polyolefins is a compromising technique. Best resolution in terms of molecular weight and molecular weight distribution requires a very low sample solution concentration in size-exclusion chromatography while best results from online infrared (IR) spectroscopy require as high concentrations as possible. The signal-to-noise ratio at the IR detector could be increased significantly after application of a bandpass filter instead of a steel mesh attenuator and furthermore influences of system instabilities could be decreased by changes in data processing. Reliable short-chain branching information in the high molecular weight section in respect to accuracy and repeatability with better chromatographic resolution could be achieved.     

A peptide co-solvent under scrutiny: self-aggregation of 2,2,2-trifluoroethanol

Trifluoroethanol (TFE) and its aggregates are studied via supersonic jet FTIR and Raman spectroscopy as well as by quantum chemistry and simple force field approaches. A multi-slit nozzle is introduced to study collisionally excited clusters. Efforts are made to extract harmonic frequencies from experiment for better comparison to theory. Based on deuteration, the OH stretching anharmonicity changes weakly upon dimerization, but increases for trimers. Among the possible dimer conformations, only an all-gauche, homoconfigurational, compact, OH-F connected structure is observed in an extreme case of chiral discrimination. Quantum tunneling assisted pathways for this surprising helicity synchronization are postulated. The oscillator coupling in hydrogen-bonded trimers is analyzed. Trans conformations of TFE start to become important for trimers and probably persist in the liquid state. Simple force fields can be refined to capture some molecular recognition features of TFE dimer, but their limitations are emphasized.     

If You Don't Have a Good Laboratory,Find a Good Volcano: Mount Vesuvius as a Natural Chemical Laboratory in Eighteenth-Century Italy

This essay that examines the role of the volcano as a chemical site in the late eighteenth century, as the “new chemistry” spread throughout the southern Italian Kingdom of Naples, resulting in lively debates. In Naples itself, these scientific debates were not confined to academies, courts, and urban spaces. In the absence of well-equipped chemical laboratories, Neapolitan scholars also carried out research on chemistry on the slopes of Mount Vesuvius, a natural site that furnished them with all the tools and substances necessary for practising chemistry. By examining various Neapolitan publications on Vesuvius and the chemical reactions and products associated with its periodic eruptions, I argue that the volcano's presence contributed to a distinctive, local approach to chemical theory and practice. Several case studies examine the ways in which proximity to Vesuvius was exploited by Neapolitan scholars as they engaged with the new chemistry, including Giuseppe Vairo, Michele Ferrara, Francesco Semmola, and Emanuele Scotti.     

Minmax due-date assignment with a time window for acceptable lead-times

In a standard DIF due-date assignment model, customers may consider late due-dates as unacceptable, i.e., if a due-date is assigned later than a pre-specified lead time, the supplier is penalized. This note extends this setting by adding a lower bound on the acceptable lead-time, reflecting e.g., the time needed by the customer for preparation of storage space. Thus, in addition to the standard earliness/tardiness penalties of jobs, our model contains penalties for early and tardy due-dates. The objective is of a minmax type, i.e. we try to minimize the highest (job and due-date) cost. An efficient O(n) solution algorithm (where n is the number of jobs) is introduced.