Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al-Salen Complexes.

The origin of stereocontrol in ring opening polymerization (ROP) of racemic lactide (rac-LA) promoted by achiral aluminium-based catalysts has been explained through DFT calculations combined with a molecular descriptor (%V) and the activation strain model (ASM-NEDA) analysis. The proposed chain end control (CEC) model suggests that the ligand framework adopts a chiral configuration mimicking the enantiomorphic site control (ESC) while also incorporating control of the last inserted monomer unit. It is found that the ligand wrapping mode around the aluminium centre is dictated by the monomer configuration (R,R-LA and S,S-LA).

The Impact of Regiodefects on the Melt-Memory of Isotactic Polypropylene.

The memory of crystalline phase in the melt of isotactic polypropylene (iPP) in regiodefective samples of iPP characterized by different concentrations regiodefects, constituted by secondary 2,1 propene units, is studied. The self-nucleation (SN) experiments have demonstrated that the presence of 2,1 regiodefects produces a strong memory of the crystalline phase in the melt that persists up to temperatures much higher than the melting temperature. The extension of the heterogeneous melt (domain II) containing self-nuclei increases with increasing the concentration of regiodefects.

Mechanistic insights on 1-butene polymerization catalyzed by homogeneous single-site catalysts: a DFT computational study.

Isotactic poly (1-butene) (iPB) is an interesting semi-crystalline thermoplastic material characterized by notable physical and mechanical attributes encompassing superior creep and stress resistance, elevated toughness, stiffness, and thermal endurance. These distinctive features position iPB as a viable candidate for specific applications; however, its widespread utilization is hindered by certain inherent limitations. Indeed, iPB manifests an intricate polymorphic behavior, and the gradual and spontaneous transition of the kinetically favored form II to the thermodynamically favored form I during aging introduces alterations to the material's properties.

Ethylene--α-Olefin Copolymers by Hydrogenation of Highly Stereoregular -1,4 Polydienes: Synthesis and Structural Characterization.

The homogeneous non-catalytic hydrogenation of several types of iso- and syndiotactic -1,4 poly(1,3-diene)s with diimide, formed by thermal decomposition of -toluene-sulfonyl-hydrazide, was examined. Perfectly alternating ethylene/1-alkene copolymers having different tacticity (i.e.

Form II to form I transition in solution-crystallized isotactic polybutene-1.

Different polymer chains in a solution or melt have different conformations with corresponding entropy at each moment, which would be confined after crystallization. Equilibrium concept-based conformation or conformational entropy depends on chain dynamics, which is related to the effect of energy on conformational changes in polymer chains. Herein, an isotactic polybutene-1 (iPB-1) crystal was crystallized from solution by adding a precipitant at various temperatures.

Combining Cyclic Units and Unsaturated Pendant Groups by Propene/1,5-Hexadiene Copolymerization Toward Functional Isotactic Polypropylene.

The precise use of a widely available and inexpensive metallocene catalyst enabled the synthesis of isotactic polypropylene copolymers characterized by the copresence of randomly distributed cyclic units in the backbone and unsaturated pendant units employing 1,5-hexadiene as comonomer. Optimization of the polymerization conditions avoided the cross-linking phenomena that negatively affects the material processing and final properties, resulting in good yields of samples featuring high molecular masses and a precisely controlled microstructure. Such polypropylene-based copolymers exhibit a broad spectrum of properties ranging from thermoplastic to surprising elastomeric behavior, with the additional value of being functionalizable by post-polymerization reactions.

Revisiting Stereoselective Propene Polymerization Mechanisms: Insights through the Activation Strain Model.

The stereoelectronic factors responsible for stereoselectivity in propene polymerization with several metallocene and post-metallocene transition metal catalysts have been revisited using a combined approach of DFT calculations, the Activation Strain Model, Natural Energy Decomposition Analysis and a molecular descriptor (%V). There are in most cases two different paths leading to the formation of stereoerrors (SE), and the classical model does not suffice to fully understand stereoregulation. Improving stereoselectivity requires raising the energies of both SE insertion transition states.

Keto-Polyethylenes with Controlled Crystallinity and Materials Properties from Catalytic Ethylene-CO-Norbornene Terpolymerization.

Recent advances in Ni(II) catalyzed, nonalternating catalytic copolymerization of ethylene with carbon monoxide (CO) enable the synthesis of in-chain keto-functionalized polyethylenes (keto-PEs) with high-density polyethylene-like materials properties. Addition of norbornene as a bulky, noncrystallizable comonomer during catalytic polymerization allows tuning of the crystallinity in these keto-PE materials by randomly incorporated norbornene units in the polymer chain, while molecular weights are not adversely affected. Such crystallinity-reduced keto-PEs are characterized as softer materials with better ductility and may therefore be more suited for, e.

Ring Opening Polymerization of Six- and Eight-Membered Racemic Cyclic Esters for Biodegradable Materials.

The low percentage of recyclability of the polymeric materials obtained by olefin transition metal (TM) polymerization catalysis has increased the interest in their substitution with more eco-friendly materials with reliable physical and mechanical properties. Among the variety of known biodegradable polymers, linear aliphatic polyesters produced by ring-opening polymerization (ROP) of cyclic esters occupy a prominent position. The polymer properties are highly dependent on the macromolecule microstructure, and the control of stereoselectivity is necessary for providing materials with precise and finely tuned properties.

Mechanism of Alternating Poly(lactic--glycolic acid) Formation by Polymerization of ()- and ()-3-Methyl Glycolide Using an Enantiopure Aluminum Complex.

The mechanism(s) of alternating PLGA synthesis by ring-opening polymerization of ()- and ()-3-methyl glycolide promoted by enantiopure aluminum complexes have been rationalized by density functional theory (DFT) calculations. The high regioselectivity of the ()-MeG polymerization is obtained by repetitive ring opening at the glycolyl site by the ()-catalyst whereas a lower regioselectivity is predicted by the ROP of ()-MeG. The behavior of the two monomers is rationalized by unveiling the active site fluxionality of the enantiopure catalyst, identifying the rate-limiting steps that encode a preference at the glycolyl site versus the lactyl site, and revealing selection of the opposite monomer enantioface.

Nationwide survey on the management of pediatric pharyngitis in Italian emergency units.

Background: Acute pharyngitis is a frequent reason for primary care or emergency unit visits in children. Most available data on pharyngitis management come from primary care studies that demonstrate an underuse of microbiological tests, a tendency to over-prescribe antibiotics and a risk of antimicrobial resistance increase. However, a comprehensive understanding of acute pharyngitis management in emergency units is lacking.

Correction to Crystal Structure of Poly(7-heptalactone).

[This corrects the article DOI: 10.1021/acs.macromol.

Synthesis, Morphology, and Crystallization Kinetics of Polyheptalactone (PHL).

Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL).

The effects of nature-based interventions on individuals' environmental behaviors: protocol for a systematic review of controlled trials.

Background: The paper presents the rationale and methods of the planned systematic review to understand the effects of nature-based interventions on individuals' environmental behaviors. There is ample evidence that experiences in nature not only enhance human well-being but also help promote people's pro-environmentalism. Nevertheless, synthesized evidence regarding the effects of nature-based interventions on individuals' environmental behaviors is lacking.

A Computational Evaluation of the Steric and Electronic Contributions in Stereoselective Olefin Polymerization with Pyridylamido-Type Catalysts.

A density functional theory (DFT) study combined with the steric maps of buried volume (%) as molecular descriptors and an energy decomposition analysis through the ASM (activation strain model)-NEDA (natural energy decomposition analysis) approach were applied to investigate the origins of stereoselectivity for propene polymerization promoted by pyridylamido-type nonmetallocene systems. The relationships between the fine tuning of the ligand and the propene stereoregularity were rationalized (e.g.

Acute Hormonal Responses to Multi-Joint Resistance Exercises with Blood Flow Restriction.

The purpose of this study was to investigate the acute effects of multi-joint resistance exercises (MJRE) with blood flow restriction on hormonal responses. Ten men participated in the study and underwent two experimental protocols in random order: four sets (30, 15, 15, and 15 reps, respectively) of MJRE (half squat and horizontal chest press) were performed with 20% of 1RM and a rest time between sets of 30 s, combined with intermittent blood flow restriction (LI + BFR protocol); and four sets (8, 8, 8, 20 reps, respectively) of the same MJRE performed with 75% of 1RM load (HI protocol), with a 90 s rest between the first three sets and 30 s between the third to the fourth set. Blood samples were collected before (PRE), immediately after (POST), and 15 min after the performance of MJRE (POST15).

Crystallization Behavior of Isotactic Propene-Octene Random Copolymers.

The crystallization behavior of random propene-octene isotactic copolymers (iPPC8) prepared with a homogeneous metallocene catalyst has been studied. Samples of iPPC8 with low octene content up to about 7 mol% were isothermally crystallized from the melt at various crystallization temperatures. The samples crystallize in mixtures of the α and γ forms of isotactic polypropylene (iPP).

Melt-Crystallizations of α and γ Forms of Isotactic Polypropylene in Propene-Butene Copolymers.

Random isotactic propene-butene copolymers (iPPC4) of different stereoregularity have been synthesized with three different homogeneous single center metallocene catalysts having different stereoselectivity. All samples crystallize from the polymerization solution in mixtures of α and γ forms, and the relative amount of γ form increases with increasing concentrations of butene and of stereodefects. All samples crystallize from the melt in mixtures of α and γ forms and the fraction of γ form increases with decreasing cooling rate.

Unconventional Stereoerror Formation Mechanisms in Nonmetallocene Propene Polymerization Systems Revealed by DFT Calculations.

An unconventional mechanism for the stereoerror formation in propene polymerization catalyzed by -symmetric salalen-M systems (M = Zr, Hf) is suggested by DFT calculations. While propagation happens with the ligand in its conformation, a change of ligand wrapping mode from to is the main source of the lower stereoselectivities obtained with Zr and Hf. This is different for the Ti analogues, where the ligand - wrapping mode does not play a role.

The Need for Sustainability, Equity, and International Exchange: Perspectives of Early Career Environmental Psychologists on the Future of Conferences.

At the 2019 and 2021 International Conference on Environmental Psychology, discussions were held on the future of conferences in light of the enormous greenhouse gas emissions and inequities associated with conference travel. In this manuscript, we provide an early career researcher (ECR) perspective on this discussion. We argue that travel-intensive conference practices damage both the environment and our credibility as a discipline, conflict with the intrinsic values and motivations of our discipline, and are inequitable.

Structure and Morphology of Crystalline Syndiotactic Polypropylene-Polyethylene Block Copolymers.

A study of the structure and morphology of diblock copolymers composed of crystallizable blocks of polyethylene (PE) and syndiotactic polypropylene (sPP) having different lengths is reported. In both analyzed samples, the PE block crystallizes first by cooling from the melt (at 130 °C) and the sPP block crystallizes after at a lower temperature. Small angle X-ray scattering (SAXS) recorded during cooling showed three correlation peaks at values of the scattering vector, = 0.

[MANAGEMENT RECOMMENDATIONS FOR DIRECT ORAL ANTICOAGULANTS (DOACs) ANTI Xa AND ANTI IIa].

Direct oral anticoagulants have emerged as the drugs that have changed the management of the antithrombotic treatment in the last 15 years. Their advantages, like a more friendly way of anticoagulation and their lower risk of bleeding, especially in the brain, have positioned these new anticoagulants as the first drug of choice in the two most frequent indications of anticoagulation, atrial fibrillation, and the venous thromboembolic disease. However, not all the patients can receive these agents, not all the direct oral anticoagulants have the same characteristics, and most importantly, not all the diseases with an indication of an anticoagulant drug can be treated with them.

Double Crystallization and Phase Separation in Polyethylene-Syndiotactic Polypropylene Di-Block Copolymers.

Crystallization and phase separation in the melt in semicrystalline block copolymers (BCPs) compete in defining the final solid state structure and morphology. In crystalline-crystalline di-block copolymers the sequence of crystallization of the two blocks plays a definitive role. In this work we show that the use of epitaxial crystallization on selected crystalline substrates allows achieving of a control over the crystallization of the blocks by inducing crystal orientations of the different crystalline phases and a final control over the global morphology.

[Guidelines for prophylaxis and anti-thrombotic treatment for patients with COVID-19. Consensus of the Latin American Cooperative Group on Hemostasis and Thrombosis (CLAHT)].

Coagulopathy and thrombosis associated with coronavirus disease 2019 (COVID-19) represent a major issue in the management of this disease. In the past months, clinical studies have demonstrated that COVID-19 patients present with a particular hypercoagulable state, in which a markedly increased D-dimer concomitant with increased levels of fibrinogen are observed. This hypercoagulable state leads to an increased risk of thrombosis, which seems to be higher among those patients with critical symptoms of COVID-19.

Syndiotactic PLA from meso-LA polymerization at the Al-chiral complex: a probe of DFT mechanistic insights.

The mechanism(s) for the formation of syndiotactic PLA by the ROP of meso-LA by a chiral-Al-complex are disclosed by DFT calculations. The contributions toward stereoselectivity have been analyzed confirming the peculiar chiral recognition for stereocontrolled ROP polymerization.