Thermolytic behavior of polydienyllithium and polystyryllithium

UV absorption spectra of thermolyzed polybutadienyl- and polyisoprenyl-lithium reveal a chromophore group previously not recognized for such systems; its absorption band at 271 nm has been assigned to a structure with three conjugated double bonds. A two-step mechanism for the formation of this trienic structure is proposed: an intermolecular metallation of associated living ends is followed by lithium hydride (LiH) elimination. Along thermolysis the presence of a dienic structure was also recognized, the latter arising from intramolecular elimination of LiH. The trienyllithium structure is also considered to be an effective species for the observed molecular weight distribution (MWD) variations. The observed different extent of high molecular weight (HMW) for polyisoprenyl- and polybutadienyl-lithium is explained on the basis of a different stability of the intermediates present along the proposed reaction mechanism. The thermolytic behavior of polystyryllithium does not provide any significant change in MWD: the disappearance of the living chain ends, UV detected, is due to an intramolecular LiH elimination which obeys first-order kinetics. The influence of temperature and of the tetrahydrofuran (THF) level on kinetic rate constants was investigated. © 1996 John Wiley & Sons, Inc.     

Packing T-joins

A consequence of Seymour's characterization of binary clutters with the Max Flow Min Cut property is that the minimum cardinality of a T-cut is equal to the largest number of edge-disjoint T-joins in every graph that cannot be T-contracted to an odd K_2,3. We give a simple “graphic” proof of this fact. © 1996 John Wiley & Sons, Inc.     

Computational maturation of a single-domain antibody against Aβ42 aggregation

The expansion of structural databases and the increase in computing power are enabling approaches for antibody discovery based on computational design. It has already been shown that it is possible to use this approach to generate antibodies for specific epitopes on challenging targets. Here we describe an application of this procedure for antibody maturation through the computational design of mutational variants of increased potency. We illustrate this procedure in the case of a single-domain antibody targeting an epitope in the N-terminal region of Aβ42, a peptide whose aggregation is closely associated with Alzheimer''s disease. We show that this approach enables the generation of an antibody variant with over 200-fold increased potency against the primary nucleation process in Aβ42 aggregation. Our results thus demonstrate that potentiated antibody variants can be obtained by computational maturation.

A computational maturation method enables the generation of an antibody variant with over 200-fold increased potency against the primary nucleation process in Aβ42 aggregation.     

Human mobility and COVID-19 initial dynamics

Nonlinear Dynamics - Countries in Europe took different mobility containment measures to curb the spread of COVID-19. The European Commission asked mobile network operators to share on a...     

Auger electron emission in proton-induced interactions in living matter: A TILDA-V Monte Carlo tracking

The present work focuses on studying the contribution of the Auger electron emission in proton-induced interactions in biological matter. The Monte Carlo track-structure code, TILDA-V, was then used for modeling the protons beams of 10 keV to 100 MeV in biological matter, namely, water vapor and hydrated DNA. The main ionizing processes are described by means of an extensive set of ab initio differential and total cross sections computed within a quantum-mechanical CDW-EIS approximation.     

Permutation Entropy-Based Interpretability of Convolutional Neural Network Models for Interictal EEG Discrimination of Subjects with Epileptic Seizures vs. Psychogenic Non-Epileptic Seizures

The differential diagnosis of epileptic seizures (ES) and psychogenic non-epileptic seizures (PNES) may be difficult, due to the lack of distinctive clinical features. The interictal electroencephalographic (EEG) signal may also be normal in patients with ES. Innovative diagnostic tools that exploit non-linear EEG analysis and deep learning (DL) could provide important support to physicians for clinical diagnosis. In this work, 18 patients with new-onset ES (12 males, 6 females) and 18 patients with video-recorded PNES (2 males, 16 females) with normal interictal EEG at visual inspection were enrolled. None of them was taking psychotropic drugs. A convolutional neural network (CNN) scheme using DL classification was designed to classify the two categories of subjects (ES vs. PNES). The proposed architecture performs an EEG time-frequency transformation and a classification step with a CNN. The CNN was able to classify the EEG recordings of subjects with ES vs. subjects with PNES with 94.4% accuracy. CNN provided high performance in the assigned binary classification when compared to standard learning algorithms (multi-layer perceptron, support vector machine, linear discriminant analysis and quadratic discriminant analysis). In order to interpret how the CNN achieved this performance, information theoretical analysis was carried out. Specifically, the permutation entropy (PE) of the feature maps was evaluated and compared in the two classes. The achieved results, although preliminary, encourage the use of these innovative techniques to support neurologists in early diagnoses.     

Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants

Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods

Polycyclic aromatic hydrocarbons (PAHs) are frequently measured in the atmosphere for air quality assessment, in biological tissues for health-effects monitoring, in sediments and mollusks for environmental monitoring, and in foodstuffs for safety reasons. In contemporary analysis of these complex matrices, gas chromatography (GC), rather than liquid chromatography (LC), is often the preferred approach for separation, identification, and quantification of PAHs, largely because GC generally affords greater selectivity, resolution, and sensitivity than LC. This article reviews modern-day GC and state-of-the-art GC techniques used for the determination of PAHs in environmental samples. Standard test methods are discussed. GC separations of PAHs on a variety of capillary columns are examined, and the properties and uses of selected mass spectrometric (MS) techniques are presented. PAH literature on GC with MS techniques, including chemical ionization, ion-trap MS, time-of-flight MS (TOF-MS), and isotope-ratio mass spectrometry (IRMS), is reviewed. Enhancements to GC, for example large-volume injection, thermal desorption, fast GC, and coupling of GC to LC, are also discussed with regard to the determination of PAHs in an effort to demonstrate the vigor and robustness GC continues to achieve in the analytical sciences.     

Spectroscopic properties in the liquid phase: combining high-level ab initio calculations and classical molecular dynamics.

We present an integrated computational tool, rooted in density functional theory, the polarizable continuum model, and classical molecular dynamics employing spherical boundary conditions, to study the spectroscopic observables of molecules in solution. As a test case, a modified OPLS-AA force field has been developed and used to compute the UV and NMR spectra of acetone in aqueous solution. The results show that provided the classical force fields are carefully reparameterized and validated, the proposed approach is robust and effective, and can also be used by nonspecialists to provide a general and powerful complement to experimental techniques.