Thermal effects on the structure and relaxation properties of poly(monocyclopentyl itaconate)

[EN] The effect of thermal treatment and subsequent chemical structural modifications on the viscoelastic and dielectric properties of PMCPI (poly(monocyclopentyl itaconate)) was studied. The low temperature relaxation (gamma-relaxation) is unaffected by the thermal history or chemical modifications. The intermediate relaxation (beta-relaxation) is shifted by about 40 degrees C to higher temperature after thermal treatment. The alpha-relaxation (related to the glass transition temperature T-g) suffers more striking changes when moving to higher temperatures.Díaz Calleja, R.; Sanchis Sánchez, MJ.; Gargallo, L.; Radic, D. (1995). Thermal effects on the structure and relaxation properties of poly(monocyclopentyl itaconate). Macromolecular Chemistry and Physics. 196(11):3789-3796. doi:10.1002/macp.1995.021961129S378937961961

Memory function on dielectric relaxation

[EN] The second-order memory function ~SOMF! for the dicyclohexylmetyl-2metyl succinate is obtained by using simple numerical manipulation of the experimental dielectric data. According to the prescription given in a previous paper @J. Chem. Phys. 109, 9057 ~1998!#, the frequency behavior of the real and imaginary parts of the SOMF is discussed in terms of the Havriliak-Negami equation of the dielectric function, and together with the three-variable model describing the evolution of the torque-autocorrelation function. Furthermore, in this paper we present the temperature dependence of the parameters, which characterize the SOMF behavior for two ester substances. © 2000 American Institute of Physics. @S0021-9606~00!51048-4#This work was supported in part by the UPV. One of the authors L. F del C. wishes to thank DGAPA-UNAM for support from Grant No. IN119200. Authors of the UPV also thank the Science and Technology Office of Spain for Grant No. MAT 1999-1127-C04-03.Díaz-Calleja, R.; García Bernabé, A.; Sanchis Sánchez, MJ.; Del Castillo, L. (2000). Memory function on dielectric relaxation. The Journal of Chemical Physics. 113(24):11258-11263. https://doi.org/10.1063/1.1326913S11258112631132

Dielectric spectroscopy of natural rubber-cellulose II nanocomposites

[EN] Nanocomposite materials obtained from natural rubber (NR) reinforced with different amounts of cellulose II nanoparticles (in the range of 0 to 30 phr) are studied by dielectric spectroscopy (DS). For comparative purposes the pure materials, NR and cellulose, are also investigated. The dielectric spectra of the nanocomposites exhibit: (a) two overlapped ¿-relaxations associated respectively with the dynamic glass transitions of NR (faster process) and of the lipid present in NR; (b) a ß-relaxation associated with local chain dynamics of cellulose and (c) a relaxation process associated to the presence of traces of water in cellulose. The spectra exhibit conductivity phenomena at low frequencies and high temperatures. The samples were also studied in the dry state. An explanation is given concerning the cellulose effect on the dielectric properties of the dry and wet nanocomposites. © 2010 Elsevier B.V.All rights reserved.The authors gratefully acknowledge CICYT for Grant No. MAT2008-06725-C03-03 and Generalitat Valenciana for Grant No. ACOMP/2010/204.Ortiz Serna, MP.; Díaz Calleja, R.; Sanchis Sánchez, MJ.; Riande, E.; Numes, R.; Martins, A.; Visconte, L. (2011). Dielectric spectroscopy of natural rubber-cellulose II nanocomposites. Journal of Non-Crystalline Solids. 357(2):598-604. doi:10.1016/j.jnoncrysol.2010.06.044S598604357

Graphene catalyzes the reversible formation of a C–C bond between two molecules

Carbon deposits are well-known inhibitors of transition metal catalysts. In contrast to this undesirable behavior, here we show that epitaxial graphene grown on Ru(0001) promotes the reversible formation of a C–C bond between −CH2CN and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ). The catalytic role of graphene is multifaceted: First, it allows for an efficient charge transfer between the surface and the reactants, thus favoring changes in carbon hybridization; second, it holds the reactants in place and makes them reactive. The reaction is fully reversible by injecting electrons with an STM tip on the empty molecular orbitals of the product. The making and breaking of the C–C bond is accompanied by the switching off and on of a Kondo resonance, so that the system can be viewed as a reversible magnetic switch controlled by a chemical reactionJ.J.N., F.C., R.M., and A.L.V.d.P. acknowledge the Ministerio de Economía y Competitividad (MINECO) project FIS2015-67367-C2-1-P and Comunidad de Madrid projects MAD2D P2013/MIT-3007 and Nanofrontmag S2013/MIT-2850. M.P., C.D., and F.M. acknowledge the MINECO project FIS2016-77889-R and computer time from the CCC-UAM and the Red Española de Supercomputación. C.D. acknowledges a Ramón y Cajal contract from MINECO (Spain). E.M.P., J.V., and B.N.-O. acknowledge the European Research Council project MINT, ERC-StG-2012-307609. IMDEA Nanoscience acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, grant SEV-2016-0686). IFIMAC acknowledges support from the “María de Maeztu” Programme for Units of Excellence in R&D (MDM-2014-0377

Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains

The synthesis, thermal and mechanical characterizations of uncrosslinked and lightly crosslinked poly(2-ethoxyethyl methacrylate) are reported. The uncrosslinked poly(2-ethoxyethyl methacrylate) exhibits in the glassy state two relaxations called in increasing order of temperature, the gamma and beta processes respectively. These are followed by a prominent glass rubber or alpha relaxation. By decreasing the chains mobility by a small amount of crosslinking, the beta relaxation disappears and the peak maximum associated with the alpha relaxation is shifted from 268 K to 278 K, at 1 Hz. An investigation of the storage relaxation modulus of the crosslinked polymer indicates two inflexion points that presumably are related to segmental motions of dangling chains of the crosslinked networks and to cooperative motions of the chains between crosslinking points. Nanodomains formed by side-groups flanked by the backbone give rise to a Maxwell Wagner Sillars relaxation in the dielectric spectra that have no incidence in the mechanical relaxation spectra.We thank Dr. J. Guzman (Madrid) for providing us with the CEOEMA sample. This work was financially supported by the DGCYT and CAM through the Grant MAT2008-06725-C03 and MAT2012-33483. In memoriam of Professor Emeritus Evaristo Riande in recognition of his contribution to Polymer Science.Carsí Rosique, M.; Sanchis Sánchez, MJ.; Díaz Calleja, R.; Riande, E.; Nugent, MJD. (2013). Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains. European Polymer Journal. 49(6):1495-1502. doi:10.1016/j.eurpolymj.2012.12.012S1495150249

CAR density influences antitumoral efficacy of BCMA CAR T cells and correlates with clinical outcome

Identification of new markers associated with long-term efficacy in patients treated with CAR T cells is a current medical need, particularly in diseases such as multiple myeloma. In this study, we address the impact of CAR density on the functionality of BCMA CAR T cells. Functional and transcriptional studies demonstrate that CAR T cells with high expression of the CAR construct show an increased tonic signaling with up-regulation of exhaustion markers and increased in vitro cytotoxicity but a decrease in in vivo BM infiltration. Characterization of gene regulatory networks using scRNA-seq identified regulons associated to activation and exhaustion up-regulated in CARHigh T cells, providing mechanistic insights behind differential functionality of these cells. Last, we demonstrate that patients treated with CAR T cell products enriched in CARHigh T cells show a significantly worse clinical response in several hematological malignancies. In summary, our work demonstrates that CAR density plays an important role in CAR T activity with notable impact on clinical response

Characteristics and Outcomes in Patients With COVID-19 and Acute Ischemic Stroke: The Global COVID-19 Stroke Registry

Recent case-series of small size implied a pathophysiological association between coronavirus disease 2019 (COVID-19) and severe large-vessel acute ischemic stroke. Given that severe strokes are typically associated with poor prognosis and can be very efficiently treated with recanalization techniques, confirmation of this putative association is urgently warranted in a large representative patient cohort to alert stroke clinicians, and inform pre- and in-hospital acute stroke patient pathways. We pooled all consecutive patients hospitalized with laboratory-confirmed COVID-19 and acute ischemic stroke in 28 sites from 16 countries. To assess whether stroke severity and outcomes (assessed at discharge or at the latest assessment for those patients still hospitalized) in patients with acute ischemic stroke are different between patients with COVID-19 and non-COVID-19, we performed 1:1 propensity score matching analyses of our COVID-19 patients with non-COVID-19 patients registered in the Acute Stroke Registry and Analysis of Lausanne Registry between 2003 and 2019. Between January 27, 2020, and May 19, 2020, 174 patients (median age 71.2 years; 37.9% females) with COVID-19 and acute ischemic stroke were hospitalized (median of 12 patients per site). The median National Institutes of Health Stroke Scale was 10 (interquartile range [IQR], 4-18). In the 1:1 matched sample of 336 patients with COVID-19 and non-COVID-19, the median National Institutes of Health Stroke Scale was higher in patients with COVID-19 (10 [IQR, 4-18] versus 6 [IQR, 3-14]), P=0.03; (odds ratio, 1.69 [95% CI, 1.08-2.65] for higher National Institutes of Health Stroke Scale score). There were 48 (27.6%) deaths, of which 22 were attributed to COVID-19 and 26 to stroke. Among 96 survivors with available information about disability status, 49 (51%) had severe disability at discharge. In the propensity score-matched population (n=330), patients with COVID-19 had higher risk for severe disability (median mRS 4 [IQR, 2-6] versus 2 [IQR, 1-4], P<0.001) and death (odds ratio, 4.3 [95% CI, 2.22-8.30]) compared with patients without COVID-19. Our findings suggest that COVID-19 associated ischemic strokes are more severe with worse functional outcome and higher mortality than non-COVID-19 ischemic strokes

Characteristics and Outcomes in Patients With COVID-19 and Acute Ischemic Stroke: The Global COVID-19 Stroke Registry.

Recent case-series of small size implied a pathophysiological association between coronavirus disease 2019 (COVID-19) and severe large-vessel acute ischemic stroke. Given that severe strokes are typically associated with poor prognosis and can be very efficiently treated with recanalization techniques, confirmation of this putative association is urgently warranted in a large representative patient cohort to alert stroke clinicians, and inform pre- and in-hospital acute stroke patient pathways. We pooled all consecutive patients hospitalized with laboratory-confirmed COVID-19 and acute ischemic stroke in 28 sites from 16 countries. To assess whether stroke severity and outcomes (assessed at discharge or at the latest assessment for those patients still hospitalized) in patients with acute ischemic stroke are different between patients with COVID-19 and non-COVID-19, we performed 1:1 propensity score matching analyses of our COVID-19 patients with non-COVID-19 patients registered in the Acute Stroke Registry and Analysis of Lausanne Registry between 2003 and 2019. Between January 27, 2020, and May 19, 2020, 174 patients (median age 71.2 years; 37.9% females) with COVID-19 and acute ischemic stroke were hospitalized (median of 12 patients per site). The median National Institutes of Health Stroke Scale was 10 (interquartile range [IQR], 4-18). In the 1:1 matched sample of 336 patients with COVID-19 and non-COVID-19, the median National Institutes of Health Stroke Scale was higher in patients with COVID-19 (10 [IQR, 4-18] versus 6 [IQR, 3-14]), P=0.03; (odds ratio, 1.69 [95% CI, 1.08-2.65] for higher National Institutes of Health Stroke Scale score). There were 48 (27.6%) deaths, of which 22 were attributed to COVID-19 and 26 to stroke. Among 96 survivors with available information about disability status, 49 (51%) had severe disability at discharge. In the propensity score-matched population (n=330), patients with COVID-19 had higher risk for severe disability (median mRS 4 [IQR, 2-6] versus 2 [IQR, 1-4], P&lt;0.001) and death (odds ratio, 4.3 [95% CI, 2.22-8.30]) compared with patients without COVID-19. Our findings suggest that COVID-19 associated ischemic strokes are more severe with worse functional outcome and higher mortality than non-COVID-19 ischemic strokes