Silent research vessels are not quiet

Behavior of herring (Clupea harengus) is stimulated by two ocean-going research vessels; respectively designed with and without regard to radiated-noise-standards. Both vessels generate a reaction pattern, but, contrary to expectations, the reaction initiated by the silent vessel is stronger and more prolonged than the one initiated by the conventional vessel. The recommendations from the scientific community on noise-reduced designs were motivated by the expectation of minimizing bias on survey results caused by vessel-induced fish behavior. In conclusion, the candidate stimuli for vessel avoidance remain obscure. Noise reduction might be necessary but is insufficient to obtain stealth vessel assets during surveys.     

Rhodium-catalyzed decarbonylation of aldoses

A catalytic procedure is described for decarbonylation of unprotected aldoses to afford alditols with one less carbon atom. The reaction is performed with the rhodium complex Rh(dppp)2Cl in a refluxing diglyme-DMA solution. A slightly improved catalyst turnover is observed when a catalytic amount of pyridine is added. Under these conditions most hexoses and pentoses undergo decarbonylation into the corresponding pentitols and tetrols in isolated yields around 70%. The reaction has been applied as the key transformation in a five-step synthesis of L-threose from D-glucose.     

Formation of dielectric layers and charge regulation in protein adsorption at biomimetic interfaces

Protein charge is an important parameter in the understanding of protein interactions and function. Proteins are subject to dynamic charge regulation, that is, the influence of the local environment (such as charged interfaces and biopolymers) on protein charge. Charge regulation is governed by differences in the dielectric and electrostatic environment between adsorbed protein and the free protein in bulk solution. In this work protein charge regulation is addressed experimentally by employing electrochemistry at interfaces between two immiscible electrolyte solutions (ITIES) as well as theoretically by developing a new protein adsorption model at ITIES. Electrochemistry at ITIES is shown to be particularly well suited to study protein charge regulation as the adsorbed protein experiences a different dielectric environment compared to the bulk phase and the external control of the water/oil potential difference allows systematic studies on how potential induced ion gradients affect protein charge. The theoretical model incorporates all the features of the experimental system and specifically takes into account protein charge regulation at ITIES as well as the impact of the formation of dielectric layers on the experimentally observed impedance. The model parameters include the protein charge-pH profile, bulk pH, and the overall potential difference. It is shown that the formation of a dielectric layer and the associated charge regulation are the main factors dictating the observed experimental behavior. Finally, the theoretical model is used to interpret literature results, and the consistency between the model and the relatively large data set suggests that the model may be used more generally for understanding and predicting protein adsorption.     

A Constraint Programming model for fast optimal stowage of container vessel bays

Container vessel stowage planning is a hard combinatorial optimization problem with both high economic and environmental impact. We have developed an approach that often is able to generate near-optimal plans for large container vessels within a few minutes. It decomposes the problem into a master planning phase that distributes the containers to bay sections and a slot planning phase that assigns containers of each bay section to slots. In this paper, we focus on the slot planning phase of this approach and present a Constraint Programming and Integer Programming model for stowing a set of containers in a single bay section. This so-called slot planning problem is NP-hard and often involves stowing several hundred containers. Using state-of-the-art constraint solvers and modeling techniques, however, we were able to solve 90% of 236 real instances from our industrial collaborator to optimality within 1 second. Thus, somewhat to our surprise, it is possible to solve most of these problems optimally within the time required for practical application.     

Synthesis and Molecular Structure of 99Tc Corroles

The first ⁹⁹Tc corroles have been synthesized and fully characterized. A single‐crystal X‐ray structure of a ⁹⁹TcO triarylcorrole revealed nearly identical geometry parameters as the corresponding ReO structure. A significant spectral shift between the Soret maxima of TcO (410–413 nm) and ReO (438–441 nm) corroles was observed and, based on two‐component spin–orbit ZORA TDDFT calculations, ascribed to relativistic effects in the Re case. The syntheses reported herein potentially pave the way toward ^99mTc‐porphyrinoid‐based radiopharmaceuticals.     

A Multivariate Analysis on the Influence of Indigenous Crude Oil Components on the Quality of Produced Water. Comparison Between Bench and Rig Scale Experiments

A matrix of 30 crude oils have been analyzed to investigate if there is any correlation between the physiochemical properties of the crude oils and the quality of the produced water. As an approach to study produced water quality, oil. and brine water (3.5 wt%) have been mixed together, and transmission profiles from the separation process have been investigated by means of Turbiscan LAb. The Turbiscan LAb enables the study of stability of colloidal dispersions without any dilution or modification of the sample. The oil-in-water emulsions (30:70) were made by mixing oil and water at low speed to be sure that they separate within a short period of time. Drop size distributions were investigated for all crude oil emulsions by using a Coulter Counter (COULTER Multisizer II). The correlations between transmission profiles and crude oil characteristics were made by using principal component analysis (PCA), a method that helps visualize the most important information contained in a data set and find combinations of variables that describe major trends. A Vortoil K-liner hydrocyclone connected to a mixing rig has been used to separate oil and water in larger scale experiments. The objective with these experiments was to compare the results with separation experiments done at bench scale. Six crude oils have been investigated at the separation rig, and both droplet size distribution and dispersed oil concentration have been performed. The main conclusions from this work are that Turbiscan LAb is a suitable technique to study the separation of oil-in-water with good reproducibility. The results from the multivariate data analysis show that the crude oils group according to if they are light or heavy and according to if they get high or low transmission. From the larger scale experiments it has been shown that the droplet sizes, oil/water density differential, and viscosity have a significant impact on separation efficiency.     

Improved pulsed broadband ultrasonic spectroscopy for analysis of liquid-particle flow

The paper contains an investigation of broadband pulsed ultrasonic spectroscopy techniques, intended for testing of suspensions, such as a liquid-particle flow containing small diameter particles. Influence of traditional and novel broadband pulse shapes on quality of frequency spectra is analysed, as well as pulse design aspects leading to an optimal shape of an ultrasonic excitation wave. Effects that may influence signal quality and method reliability in a given setup, in particular resonances and noise are discussed. Solutions for signal acquisition and averaging techniques are presented, as well as results of testing of instrumentation limits and overall performance. Results of acoustic spectroscopy measurement of a concentrated liquid-particle flow are provided. A number of experimental and numerical examples, together with comprehensive explanations, show a potential for ultrasonic attenuation spectroscopy to be a successful methodology for an on-line measurement of fluid-particle suspensions and composite non-homogeneous materials in general.     

Toward the synthesis of norzoanthamine: complete fragment assembly

The complex marine alkaloid norzoanthamine (2) was envisioned to be assembled from three key building blocks: the C1-C5 fragment A, the C6-C10 fragment B, and the C11-C24 fragment C. The synthesis of fragment A was achieved in 14 steps and 33% overall yield from (R)-gamma-hydroxymethyl-gamma-butyrolactone. Fragment B was made in two steps from PMB-protected 4-pentynol in 76% yield. The C11-C24 fragment C was made from (S)-carvone via (R)-isocarvone in 18 steps (6% overall yield). The convergent stereoselective synthesis of the entire carbon framework (C1-C24) of the target molecule was achieved via the following assemblage. Alkenyl iodide 20 derived from the C11-C24 fragment C was coupled to fragment B (C6-C10) through a high-yielding Stille coupling reaction of these two sterically very demanding coupling partners, affording the key Diels-Alder precursor 24. The intramolecular Diels-Alder reaction proceeded smoothly in excellent yield and diastereoselectivity, generating the tricyclic trans-anti-trans perhydrophenanthrene motif of norzoanthamine (C6-C24). The final fragment coupling between lithiated fragment A (C1-C5) and aldehyde 40 (C6-C24) has also been successfully accomplished affording the entire carbon framework of the natural product.     

Complexation of tauro- and glyco-conjugated bile salts with three neutral beta-CDs studied by ACE

Complexation of the bile salts (BS) taurocholate, tauro-beta-muricholate, taurodeoxycholate, taurochenodeoxycholate, glycocholate, glycodeoxycholate, and glycochenodeoxycholate common in rat, dog, and man with natural beta-CD and the chemically modified beta-CDs 2-hydroxypropyl-beta-CD and 2-O-methyl-beta-CD was studied using mobility shift ACE. The CDs were selected due to their frequent use in preformulation and drug formulation as oral excipients for the solubilization of drug substances with low aqueous solubility. ACE was demonstrated to be a feasible and efficient technique for investigation of the interactions between BS and beta-CDs. All the investigated BS possessed affinity for the three CDs with stability constants ranging from 2x10(3) to 4x10(5) M(-) (1). The requirements and assumptions related to the use of ACE for estimating high affinity stability constants were discussed. The extent and pattern of hydroxylation significantly influenced the affinity of the glyco- and tauro-conjugated BS toward the beta-CDs (chenodeoxycholates > deoxycholates > cholates) whereas the nature of the beta-CD derivatization and BS conjugation played a minor role only. The results indicate that displacement of drug substances from beta-CD inclusion complexes is likely to occur in the small intestine where BS are present potentially influencing drug bioavailability.