New bifunctional Ni H-Beta catalysts for the heterogeneous oligomerization of ethylene

[EN] The development of sustainable active and stable heterogeneous catalysts for the oligomerization of ethylene to replace the unfriendly homogenous systems based on transition metal complexes currently applied in the industry still remains a challenge. In this work we show that bifunctional catalysts comprised of Ni loaded on nanocrystalline zeolite H-Beta can efficiently catalyze the oligomerization of ethylene with high stability and selectivity to liquid oligomers under mild reaction conditions. Ni-Beta catalysts were prepared starting from a commercial nanocrystalline H-Beta sample with Si/Al ratio of 12 via both ionic exchange (1.0 2.5 wt% Ni) and incipient wetness impregnation (1.1 10.0 wt% Ni) using aqueous Ni(NO3)2 solutions, followed by air-calcination at 550 ◦C. The Ni-Beta catalysts exhibited no signs of deactivation under the studied conditions (T = 120 ◦C, Ptot = 3.5 MPa, PC2H4 = 2.6 MPa, WHSV= 2.1 h−1, TOS = 0 9 h). The conversion of ethylene increased linearly with increasing Ni loading up to ca. 2.5 wt%, irrespective of the method of Ni incorporation. Then, the conversion leveled off and attained a value of ca. 87% at higher Ni loadings (impregnated series), concurring with the development of large, XRDvisible, NiO crystallites sizing ca. 7 16 nm. Interestingly, the disappearance of Brønsted acid sites upon Ni incorporation increased linearly up to Ni contents of ca. 2.5 wt% and then leveled off, thus paralleling the activity trend. This fact indirectly suggests that Ni2+ cations replacing H+ in ion exchange positions could be the active sites responsible for the activity of Ni-Beta catalysts. Direct evidence for the nature of the active Ni sites was obtained from low temperature (−20 ◦C) CO adsorption and ethylene CO coadsorption experiments followed by FTIR. CO-FTIR results ruled out the participation of Ni+ ions and provided support for the assignation of ion exchanged Ni2+ species as the likely active sites in Ni-Beta catalysts. Additionally, most active Ni-Beta catalysts displayed a non-Schulz Flory product distribution with high selectivity to liquid oligomers (≥60 wt%) and high degree of branching due to the contribution of the hetero-oligomerization pathway involving zeolite Brønsted acid sites.This paper reports work undertaken in the context of the project “OCMOL, Oxidative Coupling of Methane followed by Oligomerization to Liquids”. OCMOL is a Large Scale Collaborative Project supported by the European Commission in the 7th Framework Programme (GA nº 228953). For further information about OCMOL see: http://www.ocmol.eu or http://www.ocmol.com. S.M. thanks ITQ for a predoctoral fellowship.Martinez Feliu, A.; Arribas Viana, MDLD.; Concepción Heydorn, P.; Moussa-Martí, S. (2013). New bifunctional Ni H-Beta catalysts for the heterogeneous oligomerization of ethylene. Applied Catalysis A General. 467:509-518. https://doi.org/10.1016/j.apcata.2013.08.021S50951846

Some Results on Sprout

Abstract. Sprout is a lightweight stream cipher proposed by Armknecht and Mikhalev at FSE 2015. It has a Grain-like structure with two State Registers of size 40 bits each, which is exactly half the state size of Grain v1. In spite of this, the cipher does not appear to lose in security against generic Time-Memory-Data Tradeoff attacks due to the novelty of its design. In this paper, we first present improved results on Key Recovery with partial knowledge of the internal state. We show that if 50 of the 80 bits of the internal state are guessed then the remaining bits along with the Secret Key can be found in a reasonable time using a SAT solver. Thereafter we show that it is possible to perform a distinguishing attack on the full Sprout stream cipher in the multiple IV setting using around 240 randomly chosen IVs on an average. The attack requires around 248 bits of memory. Thereafter we will show that for every Secret Key, there exist around 230 IVs for which the LFSR used in Sprout enters the all zero state during the Keystream generating phase. Using this observation, we will first show that it is possible to enumerate Key-IV pairs that produce keystream bits with period as small as 80. We will then outline a simple Key recovery attack that takes time equivalent to 266.7 encryptions with negligible memory requirement. This although is not the best attack reported against this cipher in terms of the Time complexity, it is the best in terms of the memory required to perform the attack

Ethane-beta-Sultam Modifies the Activation of the Innate Immune System Induced by Intermittent Ethanol Administration in Female Adolescent Rats

Intermittent ethanol abuse or ‘binge drinking’ during adolescence induces neuronal damage, which may be associated with cognitive dysfunction. To investigate the neurochemical processes involved, rats were administered either 1 g/kg or 2 g/kg ethanol in a ‘binge drinking’ regime. After only 3 weeks, significant activation of phagocytic cells in the peripheral (alveolar macrophages) and the hippocampal brain region (microglia cells) was present,as exemplified by increases in the release of pro-inflammatory cytokines in the macrophages and of iNOS in the microglia. This was associated with neuronal loss in the hippocampus CA1 region. Daily supplementation with a taurine prodrug, ethane-β-sultam, 0.028 g/kg, during the intermittent ethanol loading regime, supressed the release of the pro-inflammatory cytokines and of reactive nitrogen species, as well as neuronal loss, particularly in the rats administered the lower dose of ethanol, 1 g/kg. Plasma, macrophage and hippocampal taurine levels increased marginally after ethane-β-sultam supplementation. The ‘binge drinking’ ethanol rats administered 1 g/kg ethanol showed increased latencies to those of the control rats in their acquisition of spacial navigation in the Morris Water Maze, which was normalised to that of the controls values after ethane-β-sultam administration. Such results confirm that the administration of ethane-β-sultam to binge drinking rats reduces neuroinflammation in both the periphery and the brain, suppresses neuronal loss, and improved working memory of rats in a water maze study

Total hip arthroplasty through the direct anterior approach with and without the use of a traction table: a matched-control, retrospective, single-surgeon study.

Hip surgeons performing total hip arthroplasty (THA) through the direct anterior approach (DAA) commonly use a traction table to facilitate exposure. Even though performing THA through DAA without a traction table could be technically more demanding, this technique offers the advantage of intraoperative leg length comparison. Therefore, this study aimed to compare clinical outcomes, complication rates, component positioning, and leg length discrepancy (LLD) after THA through the DAA performed with or without a traction table. A single-surgeon continuous series of 75 patients who underwent DAA THA performed with a traction table was matched for gender, age, and BMI with 75 patients who underwent DAA THA performed without a traction table (male, 62; female, 88, with an average age of 68 years old). Clinical and radiological outcomes, intra- and postoperative complications, and LLD were retrospectively assessed. No statistically significant difference was detected in surgical time, hospital stay, Harris Hip Score (HHS), complication rates, and implant positioning between the two groups. Leg length restoration was significantly more accurate in the group performed without a traction table (2.4 ± 2 mm vs. 3.7 ± 3.1 mm; p value ≤ 0.05). No LLD > 10 mm was reported in the group performed without a traction table, whereas two cases (2.7%) were reported in those performed with a traction table. Performing THA through DAA without a traction table was associated with a significantly more accurate leg length restoration without a significant increase in the rates of intra- and postoperative complications

Functional and radiographic outcomes of reverse shoulder arthroplasty with a minimum follow-up of 10 years

Background: The use of reverse shoulder arthroplasty (RSA) is becoming increasingly prevalent. However, few studies have been published reporting the long-term outcomes of RSA. This study aims to report the clinical, radiographic, and patient-reported outcomes of the Delta Xtend reverse shoulder prosthesis, performed by a single surgeon and with a minimum follow-up of 10 years. Methods: All RSA procedures performed between 2005 and 2012 were identified. Patients were contacted and invited for a follow-up visit including clinical assessment, radiographs, and patient-reported outcome measures. Patients with a follow-up of less than 10 years were excluded. The revision-free implant survival was calculated at 10 years. Between 2005 and 2012, 119 procedures in 116 patients meeting inclusion criteria were identified. Of these patients, 35 were deceased before reaching the 10-year follow-up and 23 could not be reached. In total, 63 RSAs could be included in 61 patients (response rate: 75%). The median follow-up was 11.7 years (interquartile range [IQR]: 10.5-13.2). Results: Of the 61 patients, 7 patients underwent a revision after a median of 3 years (IQR: 0.2-9.8) during the total follow-up period. The 10-year implant survival was 94% (95% confidence interval: 84-98). At final follow-up, the median anterior elevation was 135° (IQR: 130°-160°), the median abduction was 120° (IQR: 100°-135°), and the median level reached with internal rotation was L5 (IQR: sacrum-L5). The median Auto-Constant score was 68 (IQR: 53-78), the median Subjective Shoulder Value was 80 (IQR: 70-93), and the median pain score was 0.2/10 (IQR: 0-2). In total, radiographs could be obtained in 25 patients (40%). Scapular notching occurred in 10 patients (40%), which was classified as Sirveaux-Nerot grade IV in 3 patients (12%). Ossification occurred in 10 patients (40%), and stress shielding in 2 patients (8%). Radiolucencies were observed around the humeral component in 24 patients (96%) and around the glenoid component in 13 patients (52%). Conclusion: The long-term results of RSA with a Delta Xtend prosthesis are favorable, with long-term improvement in range of motion and patient-reported outcome measures, and a satisfactory implant survival rate. Interestingly, the radiographical analysis showed high prevalence of signs associated with loosening, which did not seem to translate to high complication rates or inferior results.</p

User Experience Design for E-Voting: How mental models align with security mechanisms

This paper presents a mobile application for vote-casting and vote-verification based on the Selene e-voting protocol and explains how it was developed and implemented using the User Experience Design process. The resulting interface was tested with 38 participants, and user experience data was collected via questionnaires and semi-structured interviews on user experience and perceived security. Results concerning the impact of displaying security mechanisms on UX were presented in a complementary paper. Here we expand on this analysis by studying the mental models revealed during the interviews and compare them with theoretical security notions. Finally, we propose a list of improvements for designs of future voting protocols.Comment: E-Vote-ID 2019 TalTech Proceeding

Dissection of the transcriptional regulation of grape ASR and response to glucose and abscisic acid

Despite the fact that the precise physiological function of ASRs [abscisic acid (ABA), stress, ripening] remains unknown, they have been suggested to play a dual role in the plant response to environmental cues, as highly hydrophilic proteins for direct protection, as well as transcription factors involved in the regulation of gene expression. To investigate further the biological positioning of grape ASR in the hormonal and metabolic signal network, three promoters corresponding to its cDNA were isolated and submited to a detailed in silico and functional analysis. The results obtained provided evidence for the allelic polymorphism of the grape ASR gene, the organ-preferential expression conferred on the GUS reporter gene, and the specific phloem tissue localization revealed by in situ hybridization. The study of glucose and ABA signalling in its transcriptional control, by transfection of grape protoplasts using the dual luciferase system, revealed the complexity of ASR gene expression regulation. A model was proposed allowing a discussion of the place of ASR in the fine tuning of hormonal and metabolic signalling involved in the integration of environmental cues by the plant organism