Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

hyperbranched polyester soft segments (HB PU) with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylol)propionic acid of the fourth pseudo-generation (Boltorn H40) and hexamethylene (HDI) or isophorone diisocyanate (IPDI). The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios r_NCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures

Estimating subseasonal variability and trends in global atmosphere using reanalysis data

A new measure of subseasonal variability is introduced that provides a scale-dependent estimation of vertically and meridionally integrated atmospheric variability in terms of the normal modes of linearized primitive equations. Applied to the ERA-Interim data, the new measure shows that subseasonal variability decreases for larger zonal wave numbers. Most of variability is due to balanced (Rossby mode) dynamics but the portion associated with the inertio-gravity (IG) modes increases as the scale reduces. Time series of globally integrated variability anomalies in ERA-Interim show an increase in variability after year 2000. In recent years the anomalies have been about 2% above the 1981–2010 average. The relative increase in variability projecting on the IG modes is larger and more persistent than for the Rossby modes. Although the IG part is a small component of the subseasonal variability, it is an important effect likely reflecting the observed increase in the tropical precipitation variability. ©2018. The Authors

An assessment of scale-dependent variability and bias in global prediction models

The paper presents a method for the scale-dependent validation of the spatio-temporal variability in global weather or climate models and for their bias quantification in relation to dynamics. The method provides a relationship between the bias and simulated spatial and temporal variance by a model in comparison with verifying reanalysis data. For the low resolution (T30L8) subset of ERA-20C data, it was found that 80–90 (depending on season) of the global interannual variance is at planetary scales (zonal wavenumbers k = 0−3), and only about 1 of the variance is at scales with k> 7. The reanalysis is used to validate a T30L8 GCM in two configurations, one with the prescribed sea-surface temperature (SST) and another using a slab ocean model. Although the model with the prescribed SST represents the average properties of surface fields well, the interannual variability is underestimated at all scales. Similar to variability, model bias is strongly scale dependent. Biases found in the experiment with the prescribed SST are largely increased in the experiment using a slab ocean, especially in k= 0 , in scales with missing variability and in seasons with poorly simulated energy distribution. The perfect model scenario (a comparison between the GCM coupled to a slab ocean vs. the same model with prescribed SSTs) shows that the representation of the ocean is not critical for synoptic to subsynoptic variability, but essential for capturing the planetary scales. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature

Composition, morphology and structure of DLPLG/HAp nanocomposite fabricated in the field of ultrasound

Poster presented at the Women in Nano Winter School, Kranjska Gora, Slovenija, 7-9. februar 2008

Karboksilirani poliuretani s visoko razgranatim poliesterskim mekanim segmentima

hyperbranched polyester soft segments (HB PU) with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylol)propionic acid of the fourth pseudo-generation (BoltornŽ H40) and hexamethylene (HDI) or isophorone diisocyanate (IPDI). The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young\u27s modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.Rad prikazuje sintezu i karakterizaciju poliuretana s mekanim segmentima od visoko razgranatoga poliestera (HB PU) s funkcionalnim karboksilnim skupinama s namjenom pripreme stabilnih disperzija HB PU. Za sintezu karboksiliranih HB PU upotrijebili smo visoko razgranati poliester na osnovi 2,2-bis(metilol)propionske kiseline četvrte pseudo-generacije (Boltorn H40) i heksametilen-diizocijanat (HDI) ili izoforon-diizocijanat (IPDI). Reaktivnost visoko razgranatog poliestra s HDI-om bila je niža od očekivane, vjerojatno zbog postojećih manje reaktivnih hidroksilnih skupina u linearnim jedinicama. Reakcijske smjese gelirale su kod množinskog omjera rNCO/OH = 1:2 i 1:4. HB PU sintetizirali smo iz djelimično preostaloga visoko razgranatoga poliestera s nižom -OH funkcionalnosti. Karboksilne skupine smo u lanac HB PU uveli s esterifikacijom neizreagiranih hidroksilnih skupina s anhidridom cis-1,2-cikloheksandikarboksilne kiseline. Vodene disperzije HB PU bile su stabilne najmanje dva mjeseca, filmovi su bili krhki. Ispitivanja na vučnu čvrstoću i na Youngov modul elastičnosti su pokazali da su se iznosi kod smjesa linearnoga i HB PU s povećavajućim udjelom HB PU se smanjivali, dok je naprezanje na rastezanje do loma ostalo nepromijenjeno, što smo objasnili s manje gustim slaganjem lanaca zbog više otvorenih drvenastih visoko razgranatih struktura

Chemical recycling of plastics assisted by microwave multi-frequency heating

Handling plastic waste through recycling allows extending the life of polymeric materials, avoiding recurrence to incineration or landfilling. In contrast with traditional mechanical recycling technologies, chemical recycling enables the obtention of the virgin monomers by means of depolymerisation to create new polymers with the same mechanical and thermal properties as the originals. Research presented in this paper is part of the polynSPIRE project (Horizon 2020 European funding programme) and develops and scales-up a heated reactor to carry out the depolymerisation of polyamide-6 (PA6), polyamide-6, 6 (PA66) and polyurethane (PU) using microwave (MW) technology as the heating source. The purpose is to design and optimize a MW reactor using up to eight ports emitting electromagnetic waves. Finite element method (FEM) simulation and optimisation are used to design the reactor, considering as parameters the data obtained from experimental dielectric testing and lab-scale characterisation of the processes and materials studied. Two different COMSOL Multiphysics modules are involved in this work: Radio Frequency (RF) and Chemical Reaction Engineering (RE), to simulate the reactor cavity using two frequency levels (915 MHz and 2.45 GHz) with a power level of 46 kW, and the chemical depolymerisation process, respectively. A sensitivity study has been performed on key parameters such as the frequency, the number of ports, and position inside the reactor to consolidate the final design. It is expected that these results assist in the design and scale-up of microwave technology for the chemical recycling of plastics, and for the large-scale deployment of this sustainable recovery alternative. © 2021 The Author

The Intricacies of Identifying Equatorial Waves

Equatorial waves (EWs) are synoptic- to planetary-scale propagating disturbances at low latitudes with periods from a few days to several weeks. Here, this term includes Kelvin waves, equatorial Rossby waves, mixed Rossby–gravity waves, and inertio-gravity waves, which are well described by linear wave theory, but it also other tropical disturbances such as easterly waves and the intraseasonal Madden–Julian Oscillation with more complex dynamics. EWs can couple with deep convection, leading to a substantial modulation of clouds and rainfall. EWs are amongst the dynamic features of the troposphere with the longest intrinsic predictability, and models are beginning to forecast them with an exploitable level of skill. Most of the methods developed to identify and objectively isolate EWs in observations and model fields rely on (or at least refer to) the adiabatic, frictionless linearized primitive equations on the sphere or the shallow-water system on the equatorial -plane. Common ingredients to these methods are zonal wave-number–frequency filtering (Fourier or wavelet) and/or projections onto predefined empirical or theoretical dynamical patterns. This paper gives an overview of six different methods to isolate EWs and their structures, discusses the underlying assumptions, evaluates the applicability to different problems, and provides a systematic comparison based on a case study (February 20–May 20, 2009) and a climatological analysis (2001–2018). In addition, the influence of different input fields (e.g., winds, geopotential, outgoing long-wave radiation, rainfall) is investigated. Based on the results, we generally recommend employing a combination of wave-number–frequency filtering and spatial-projection methods (and of different input fields) to check for robustness of the identified signal. In cases of disagreement, one needs to carefully investigate which assumptions made for the individual methods are most probably not fulfilled. This will help in choosing an approach optimally suited to a given problem at hand and avoid misinterpretation of the results

A comparative study of the hydrogen-bonding patterns and prototropism in solid 2-thiocytosine (potential antileukemic agent) and cytosine, as studied by 1H-14N NQDR and QTAIM/ DFT

A potential antileukemic and anticancer agent, 2-thiocytosine (2-TC), has been studied experimentally in the solid state by 1H-14N NMR-NQR double resonance (NQDR) and theoretically by the quantum theory of atoms in molecules (QTAIM)/density functional theory (DFT). Eighteen resonance frequencies on 14N were detected at 180 K and assigned to particular nitrogen sites (−NH2, –N=, and –NH–) in 2-thiocytosine. Factors such as the nonequivalence of molecules (connected to the duplication of sites) and possible prototropic tautomerism (capable of modifying the type of site due to proton transfer) were taken into account during frequency assignment. The result of replacing oxygen with sulfur, which leads to changes in the intermolecular interaction pattern and molecular aggregation, is discussed. This study demonstrates the advantages of combining NQDR and DFT to extract detailed information on the H-bonding properties of crystals with complex H-bonding networks. Solid-state properties were found to have a profound impact on the stabilities and reactivities of both compounds

Supramolecular synthon pattern in solid clioquinol and cloxiquine (APIs of antibacterial, antifungal, antiaging and antituberculosis drugs) studied by 35Cl NQR, 1H-17O and 1H-14N NQDR and DFT/QTAIM

The quinolinol derivatives clioquinol (5-chloro-7-iodo-8-quinolinol, Quinoform) and cloxiquine (5-chloro-8-quinolinol) were studied experimentally in the solid state via 35Cl NQR, 1H-17O and 1H-14N NQDR spectroscopies, and theoretically by density functional theory (DFT). The supramolecular synthon pattern of O–H···N hydrogen bonds linking dimers and π–π stacking interactions were described within the QTAIM (quantum theory of atoms in molecules) /DFT (density functional theory) formalism. Both proton donor and acceptor sites in O–H···N bonds were characterized using 1H-17O and 1H-14N NQDR spectroscopies and QTAIM. The possibility of the existence of O–H···H–O dihydrogen bonds was excluded. The weak intermolecular interactions in the crystals of clioquinol and cloxiquine were detected and examined. The results obtained in this work suggest that considerable differences in the NQR parameters for the planar and twisted supramolecular synthons permit differentiation between specific polymorphic forms, and indicate that the more planar supramolecular synthons are accompanied by a greater number of weaker hydrogen bonds linking them and stronger π···π stacking interactions