Search results for: reactivity insertion

Authors: Ji Hoon Kim, Jong Man Kim, Hyung Woo Lee, Soo Hyung Kim

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The applications of nanoenergetic materials (nEMs) could be extended by developing more convenient and reliable ignition methods. However, the underwater ignition of nEMs is a significant challenge because water perturbs the reactants prior to ignition and also quenches the subsequent combustion reaction of nEMs upon ignition. In this study, we developed flash and laser-ignitable nEMs for underwater explosion. This was achieved by adding various carbon nanotubes (CNTs) as the optical igniter into an nEM matrix, composed of Al/CuO nanoparticles. The CNTs absorb the irradiated optical energy and rapidly convert it into thermal energy, and then the thermal energy is concentrated to ignite the core catalysts and neighboring nEMs. The maximum burn rate was achieved by adding 1 wt% CNTs into the nEM matrix. The burn rate significantly decreased with increasing amount of CNTs (≥ 2 wt%), indicating that the optical ignition and controlled-explosion reactivity of nEMs are possible by incorporating an appropriate amount of CNTs.

Keywords: nanoenergetic materials, carbon nanotubes, optical ignition, tunable explosion

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Authors: Kewei Fan, Sihong Liu, Yi Pik Cheng

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This paper aims to analyse the failure behaviour of the retaining wall constructed with soil bags that are formed by filling river sand into woven bags (geosynthetics). Model tests were conducted to obtain the failure mode of the wall, and shear tests on two-layers and five-layers of soil bags were designed to investigate the mechanical characteristics of the interface of soil bags. The test results show that the slip surface in the soil bags-constructed retaining wall is ladder-like due to the inter-layer insertion of soil bags, and the wall above the ladder-like surface undergoes a rigid body translation. The insertion strengthens the shear strength of two-layer staggered-stacked soil bags. Meanwhile, it affects the shape of the slip surface of the five-layer staggered-stacked soil bags. Finally, the interlayer resisting friction of soil bags is found to be related to the shape of the slip surface.

Keywords: geosynthetics, retaining wall, soil bag, failure mode, interface, shear strength

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: Raj Raghupathy

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Recurrent Spontaneous Miscarriage (RSM) is a common form of pregnancy loss, 50% of which are due to ‘unexplained’ causes. Evidence exists to suggest that RSM may be caused by immunologic factors such as cytokines which are critical molecules of the immune system, with an impressive array of capabilities. An association appears to exist between Th2-type reactivity (mediated by Th2 or anti-inflammatory cytokines) and normal, successful pregnancy, and between unexplained RSM and Th1 cytokine dominance. If pro-inflammatory cytokines are indeed associated with pregnancy loss, the suppression of these cytokines, and thus the ‘redirection’ of maternal reactivity, may help prevent cytokine-mediated pregnancy loss. The objective of this study was to explore the possibility of modulating cytokine production using Dydrogesterone (Duphaston®), an orally-administered progestogen. Peripheral blood mononuclear cells from 34 women with a history of at least 3 unexplained recurrent miscarriages were stimulated in vitro with a mitogen (to elicit cytokine production) in the presence and absence of dydrogesterone. Levels of selected pro- and anti-inflammatory cytokines produced by peripheral blood mononuclear cells were measured after exposure to these progestogens. Dydrogesterone down-regulates the production of pro-inflammatory cytokines and up-regulates the production of anti-inflammatory cytokines. The ratios of Th2 to Th1 cytokines are markedly elevated in the presence of dydrogesterone, indicating a shift from potentially harmful maternal Th1 reactivity to a more pregnancy-conducive Th2 profile. We used a progesterone receptor antagonist to show that this cytokine-modulating effect of dydrogesterone is mediated via the progesterone receptor. Dydrogesterone also induces the production of the Progesterone-Induced Blocking Factor (PIBF); lymphocytes exposed to PIBF produce higher levels of Th2 cytokines, affecting a Th1 → Th2 cytokine shift which could be favourable to the success of pregnancy. We conclude that modulation of maternal cytokine production profiles is possible with dydrogesterone which has the merits that it can be administered orally and that it is safe.

Keywords: cytokines, dydrogesterone, progesterone, recurrent spontaneous miscarriage

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Authors: Erin M. Durke, Monica L. McEntee, Meilu He, Suresh Dhaniyala

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Aerosols are one of the most important and significant surfaces in the atmosphere. They can influence weather, absorption, and reflection of light, and reactivity of atmospheric constituents. A notable feature of aerosol particles is the presence of a surface charge, a characteristic imparted via the aerosolization process. The existence of charge can complicate the interrogation of aerosol particles, so many researchers remove or neutralize aerosol particles before characterization. However, the charge is present in real-world samples, and likely has an effect on the physical and chemical properties of an aerosolized material. In our studies, we aerosolized different materials in an attempt to characterize the charge imparted via the aerosolization process and determine what impact it has on the aerosolized materials’ properties. The metal oxides, TiO₂ and SiO₂, were aerosolized expulsively and then characterized, using several different techniques, in an effort to determine the surface charge imparted upon the particles via the aerosolization process. Particle charge distribution measurements were conducted via the employment of a custom scanning mobility particle sizer. The results of the charge distribution measurements indicated that expulsive generation of 0.2 µm SiO₂ particles produced aerosols with upwards of 30+ charges on the surface of the particle. Determination of the degree of surface charging led to the use of non-traditional techniques to explore the impact of additional surface charge on the overall reactivity of the metal oxides, specifically TiO₂. TiO₂ was aerosolized, again expulsively, onto a gold-coated tungsten mesh, which was then evaluated with transmission infrared spectroscopy in an ultra-high vacuum environment. The TiO₂ aerosols were exposed to O₂, H₂, and CO, respectively. Exposure to O₂ resulted in a decrease in the overall baseline of the aerosol spectrum, suggesting O₂ removed some of the surface charge imparted during aerosolization. Upon exposure to H₂, there was no observable rise in the baseline of the IR spectrum, as is typically seen for TiO₂, due to the population of electrons into the shallow trapped states and subsequent promotion of the electrons into the conduction band. This result suggests that the additional charge imparted via aerosolization fills the trapped states, therefore no rise is seen upon exposure to H₂. Dosing the TiO₂ aerosols with CO showed no adsorption of CO on the surface, even at lower temperatures (~100 K), indicating the additional charge on the aerosol surface prevents the CO molecules from adsorbing to the TiO₂ surface. The results observed during exposure suggest that the additional charge imparted via aerosolization impacts the interaction with each probe gas.

Keywords: aerosols, charge, reactivity, infrared

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Authors: Caroline Alice Rouget-Virbel, F. Dean Toste

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Heterobimetallic systems have been precedented in a wide array of bioinorganic and heterogeneous catalytic settings, in which cooperative bond-breaking and bond-forming events mediated by neighboring metal sites have been proposed but are challenging to study and characterize. Heterodinuclear transition-metal catalysis has recently emerged as a promising strategy to tackle challenging chemical transformations, including C−C and C−X couplings as well as small molecule activation. It has been shown that these reactions can traverse nontraditional mechanisms, reactivities, and selectivities when homo- and heterobimetallic systems are employed. Moreover, stoichiometric studies of transmetallation from gold complexes have demonstrated that R transfer from PPh3–Au(I)R to Cp- and Cp*-ligated group 8/9 complexes is a viable elementary step. With these considerations in mind, we hypothesized that heterobimetallic Au–M complexes could serve as a viable and tunable catalyst platform to explore mechanisms and reactivity. In this work, heterobimetallic complexes containing Au(I) centers tethered to Ir(III) and Rh(III) piano stool moieties were synthesized and characterized. Preliminary application of these complexes to a catalytic allylic arylation reaction demonstrates bimetallic cooperativity relative to their monomeric metal components.

Keywords: heterobimetallic, catalysis, gold, rhodium

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Authors: Suresh Vanguri, Suresh Palla, K. V. Kalyani, S. K. Chaturvedi, B. N. Mohapatra

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Enhancing the fly ash utilization in the manufacture of cement is identified as one of the key areas to mitigate the Green House Gas emissions from the cement industry. Though increasing the fly ash content in cement has economic and environmental benefits, it results in a decrease in the compressive strength values, particularly at early ages. Quality of clinker and fly ash were identified as predominant factors that govern the extent of absorption of fly ash in the manufacturing of cement. This paper presents systematic investigations on the effect of clinker and fly ash quality on the properties of resultant cement. Since mechanical activation alters the physicochemical properties such as particle size distribution, surface area, phase morphology, understanding the variation of these properties with activation is required for its applications. The effect of mechanical activation on fly ash surface area, specific gravity, flow properties, lime reactivity, comparative compressive strength (CCS), reactive silica and mineralogical properties were also studied. The fineness of fly ash was determined by Blaine’s method, specific gravity, lime reactivity, CCS were determined as per the method IS 1727-1967. The phase composition of fly ash was studied using the X-ray Diffraction technique. The changes in the microstructure and morphology with activation were examined using the scanning electron microscope. The studies presented in this paper also include evaluation of Portland Pozzolana Cement (PPC), prepared using high volume fly ash. Studies are being carried out using clinker from cement plants located in different regions/clusters in India. Blends of PPC containing higher contents of activated fly ash have been prepared and investigated for their chemical and physical properties, as per Indian Standard procedures. Changes in the microstructure of fly ash with activation and mechanical properties of resultant cement containing high volumes of fly ash indicated the significance of optimization of the quality of clinker and fly ash fineness for better techno-economical benefits.

Keywords: flow properties, fly ash enhancement, lime reactivity, microstructure, mineralogy

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Authors: Abraham Finkelman

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Computerized Surgical Guides have been proven to be a predictable way to perform dental implants, with a relatively high accuracy in comparison to a treatment plan. When using the CSG Bone supported, it allows us to make the necessary changes of the hard tissue prior to the implant placement and after the implant placement. The CSG gives us an accurate position for the drilling, and during the implant placement it allows us to alter the vertical position of the implant altering the final position of the abutment and avoiding any risk of any damage to the adjacent anatomical structures. Any Changes required to the bone level can be done prior to the fixation of the CSG using a reduction guide, which incur extra surgical fees and the need of a second surgical guide. Any changes of the bone level after the implant placement are at the risk of damaging the implant neck surface. The technique consists of a universal system that allows us to remove the excess bone around the implant sockets prior to the implant placement which then enables us to place the implant in the vertical position with accuracy as planned with the CSG. The systems consist of a hollow pin of different sizes and diameters. Depending on the implant system that we are using. Length sizes are from 6mm-16mm and a diameter of 2.6mm-4.8mm. Upon the completion of the drilling, the pin is then inserted into the implant socket-using the insertion tool. Once the insertion tool has unscrewed the pin, we can continue with the bone reduction. The bone reduction can be done using conventional methods upon the removal of all the excess bone around the pin. The insertion tool is then screwed into the pin and the pin is then removed. We now, have the new bone level at the crest of the implant socket which is our mark for the vertical position of the implant. In some cases, when we are locating the implant very close to anatomical structures, any form of deviation to the vertical position of the implant during the surgery, can cause damage to such anatomical structures, creating irreversible damages such as paresthesia or dysesthesia of the mandibular nerve. If we are planning for immediate loading and we have done our temporary restauration in base of our computerized plan, deviation in the vertical position of the implant will affect the position of the abutment, affecting the accuracy of the temporary prosthesis, extending the working time till we adapt the prosthesis to the new position.

Keywords: bone reduction, computer aided navigation, dental implant placement, surgical guides

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Authors: S. Haque, M. Kanapathy, E. Bollen, I. Younis, A. Mosahebi

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Background: Implant loss due to infection is the most devastating complication of implant-based breast reconstruction. The use of negative pressure wound therapy with instillation (NPWTi) for salvage of infected implant-based breast reconstructions has shown promising results to allow early reinsertion of a new implant as an alternative to current management of delayed reinsertion. This study compares the cost implication of NPWTi against current management of delayed reinsertion of infected breast implants. Methods: 20 cases of an infected breast implant treated with NPWTi (V.A.C. VERAFLO™ Therapy) followed by early re-insertion of a new implant were compared with 20 cases who had delayed reinsertion (non-NPWTi). Average cost per person was calculated using total operative expenses, cost of inpatient stay, cost of investigations, cost of antibiotics, and cost of outpatient visits. Results: Treatment with NPWTi allowed for earlier re-insertion of a new implant (NPWTi: 9.04 ± 2.92 days vs. non-NPWTi: 236.25 ± 123.89 days). The average cost per patient for NPWTi and non-NPWTi was £14,343.13 ± £2,786.70 and £8,920.31 ± £3,005.73 respectively. All patients treated with NPWTi had one admission and spent 11.9 ± 4.1days as an inpatient while non-NPWTi patients had 2.1 ± 0.3 admissions with total length of inpatient stay of 7.1 ± 5.8days. Patients treated with NPWTi had more surgeries (NPWTi: 3.35 ± 0.81 vs. non-NPWTi: 2.2 ± 0.41), however 3 non-NPWTi cases required flap reconstruction. Patients treated with NPWTi had fewer total outpatient visits (NPWTi: 12 ± 6 vs. non-NPWTi: 14.2 ± 6.3). Conclusion: Patients treated with NPWTi incurred higher average cost per patient, longer inpatient stay, and more procedures; however, had early re-insertion of new implants and fewer admissions and outpatient visits. A further study on patient-reported outcome is essential to compare cost against patient benefit.

Keywords: breast reconstruction, cost evaluation, infection, negative pressure wound therapy

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Authors: Sylvain Caillol, Ghislain David

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Phenolic resins are industrially used in a wide range of applications from commodity and construction materials to high-technology aerospace industry. They are mainly produced from the reaction between phenolic compounds and formaldehyde. Nevertheless, formaldehyde is a highly volatile and hazardous compound, classified as a Carcinogenic, Mutagenic and Reprotoxic chemical (CMR). Vanillin is a bio-based and non-toxic aromatic aldehyde compound obtained from the abundant lignin resources. Also, its aromaticity is very interesting for the synthesis of phenolic resins with high thermal stability. However, because of the relatively low reactivity of its aldehyde function toward phenolic compounds, it has never been used to synthesize phenolic resins. We developed innovative functionalization reactions and designed new bio-based aromatic aldehyde compounds from vanillin. Those innovative compounds present improved reactivity toward phenolic compounds compared to vanillin. Moreover, they have target structures to synthesize highly cross-linked phenolic resins with high aromatic densities. We have obtained phenolic resins from substituted vanillin, thus without the use of any aldehyde compound classified as CMR. The analytical tests of the cured resins confirmed that those bio-based resins exhibit high levels of performance with high thermal stability and high rigidity properties

Keywords: phenolic resins, formaldehyde-free, vanillin, bio-based, non-toxic

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Authors: Brian J. Graham, Ronald T. Raines

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The presence of a nearly vacant p orbital on boron endows boronic acids with unique abilities as a catalyst and ligand. An organocatalytic process has been developed for the conversion of biomass-derived sugars to 5-hydroxymethylfurfural, which is a platform chemical. Specifically, 2-carboxyphenylboronic acid (2-CPBA) has been shown to be an optimal catalyst for this process, promoting the desired transformation in the absence of metals. The attributes of 2-CPBA as a catalyst led to additional investigations of its structure and reactivity. 2-CPBA was found to exist as a cyclized benzoxaborolone adduct rather than a free carboxylic acid. This cyclization has profound consequences for the oxidative stability of the boronic acid. Stereoelectronic effects within the oxaborolone ring destabilize the oxidation transition state by reducing electron donation from the cyclic oxygen to the developing p orbital on boron. That leads to a 10,000-fold increase in oxidative stability while maintaining the normal reactivity of boronic acids toward diols (e.g., carbohydrates) and nucleophiles in proteins while also presenting numerous hydrogen-bond accepting and donating groups. Thus, benzoxaborolones are useful in catalysis, chemical biology, medicinal chemistry, and allied fields.

Keywords: bioisosteres, boronic acid, catalysis, oxidative stability, pharmacophore, stereoelectronic effects

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Authors: Martin Juckel

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Probably no other field of inorganic chemistry has undergone such a rapid development in the past two decades than the low oxidation state chemistry of main group elements. This rapid development has only been possible by the development of new bulky ligands. In case of our research group, super-bulky monodentate amido ligands and β-diketiminate ligands have been used to a great success. We first synthesized the unprecedented magnesium(I) dimer [ᴹᵉˢNacnacMg]₂ (ᴹᵉˢNacnac = [(ᴹᵉˢNCMe)₂CH]-; Mes = mesityl, which has since been used both as reducing agent and also for the synthesis of new metal-magnesium bonds. In case of the zinc bromide precursor [L*ZnBr] (L*=(N(Ar*)(SiPri₃); (Ar* = C₆H₂{C(H)Ph₂}₂Me-2,6,4, the reduction with [ᴹᵉˢNacnacMg]₂ led to such a metal-magnesium bond. This [L*ZnMg(ᴹᵉˢNacnac)] compound can be seen as an ‘inorganic Grignard reagent’, which can be used to transfer the metal fragment onto other functional groups or other metal centers; just like the conventional Grignard reagent. By simple addition of (TBoN)GeCl (TBoN = N(SiMe₃){B(DipNCH)₂) to the aforesaid compound, we were able to transfer the amido-zinc fragment to the Ge center of the germylene starting material and to synthesize the first example of a germanium(II)-zinc bond: [:Ge(TBoN)(ZnL*)]. While these reactions typically led to complex product mixture, [:Ge(TBoN)(ZnL*)] could be isolated as dark blue crystals in a good yield. This new compound shows interesting reactivity towards small molecules, especially dihydrogen gas. This is of special interest as dihydrogen is one of the more difficult small molecules to activate, due to its strong (BDE = 108 kcal/mol) and non-polar bond. In this context, the interaction between H₂ σ-bond with the tetrelylene p-Orbital (LUMO), with concomitant donation of the tetrelylene lone pair (HOMO) into the H₂ σ* orbital are responsible for the activation of dihydrogen gas. Accordingly, the narrower the HOMO-LUMO gap of tertelylene, the more reactivity towards H₂ it typically is. The aim of a narrow HOMO-LUMO gap was reached by transferring electropositive substituents respectively metal substituents with relatively low Pauling electronegativity (zinc: 1.65) onto the Ge center (here: the zinc-amido fragment). In consideration of the unprecedented reactivity of [:Ge(TBoN)(ZnL*)], a computational examination of its frontier orbital energies was undertaken. The energy separation between the HOMO, which has significant Ge lone pair character, and the LUMO, which has predominantly Ge p-orbital character, is narrow (40.8 kcal/mol; cf.∆S-T= 24.8 kcal/mol), and comparable to the HOMO-LUMO gaps calculated for other literature known complexes). The calculated very narrow HOMO-LUMO gap for the [:Ge(TBoN)(ZnL*)] complex is consistent with its high reactivity, and is remarkable considering that it incorporates a π-basic amide ligand, which are known to raise the LUMO of germylenes considerably.

Keywords: activation of dihydrogen gas, narrow HOMO-LUMO gap, first germanium(II)-zinc bond, inorganic Grignard reagent

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Authors: S. U. Khan, T. Ayub, N. Shafiq

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The properties of locally produced metakaolin (MK) as cement replacing material and the comparison of reactivity with commercially available micro-silica have been investigated. Compressive strength, splitting tensile strength, and load-deflection behaviour under bending are the properties that have been studied. The amorphous phase of MK with micro-silica was compared through X-ray diffraction (XRD) pattern. Further, interfacial transition zone of concrete with micro-silica and MK was observed through Field Emission Scanning Electron Microscopy (FESEM). Three mixes of concrete were prepared. One of the mix is without cement replacement as control mix, and the remaining two mixes are 10% cement replacement with micro-silica and MK. It has been found that MK, due to its irregular structure and amorphous phase, has high reactivity with portlandite in concrete. The compressive strength at early age is higher with MK as compared to micro-silica. MK concrete showed higher splitting tensile strength and higher load carrying capacity as compared to control and micro-silica concrete at all ages respectively.

Keywords: metakaolin, compressive strength, splitting tensile strength, load deflection, interfacial transition zone

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Authors: Fu-Chien Hung, Chi‐Wen Liang

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Background: People who suffer from chronic fatigue syndrome (CFS) frequently complain about continuous tiredness, weakness or lack of strength, but without apparent organic etiology. The prevalence rate of the CFS is nearly from 3% to 20%, yet more than 80% go undiagnosed or misdiagnosed as depression. The biopsychosocial model has suggested the associations among the CFS, depressive syndrome, and stress. This study aimed to investigate the difference between individuals with the CFS and with the depressive syndrome on psychophysiological responses under stress. Method: There were 23 participants in the CFS group, 14 participants in the depression group, and 23 participants in the healthy control group. All of the participants first completed the measures of demographic data, CFS-related symptoms, daily life functioning, and depressive symptoms. The participants were then asked to perform a stressful cognitive task. The participants’ psychophysiological responses including the HR, BVP and SC were measured during the task. These indexes were used to assess the reactivity and recovery rates of the automatic nervous system. Results: The stress reactivity of the CFS and depression groups was not different from that of the healthy control group. However, the stress recovery rate of the CFS group was worse than that of the healthy control group. Conclusion: The results from this study suggest that the CFS is a syndrome which can be independent from the depressive syndrome, although the depressive syndrome may include fatigue syndrome.

Keywords: chronic fatigue syndrome, depression, stress response, misdiagnosis

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Authors: Masoumeh Ghorbania, Falk Liebnerb, Hendrikus W.G. van Herwijnenc, Johannes Konnertha

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Phenol formaldehyde (PF) resins are widely used as wood adhesives for variety of industrial products such as plywood, laminated veneer lumber and others. Lignin as a main constituent of wood has become well-known as a potential substitute for phenol in PF adhesives because of their structural similarity. During the last decades numerous research approaches have been carried out to substitute phenol with pulping-derived lignin, whereby the lower reactivity of resins synthesized with shares of lignin seem to be one of the major challenges. This work reports about a systematic screening of different types of lignin (plant origin and pulping process) for their suitability to replace phenol in phenolic resins. Lignin from different plant sources (softwood, hardwood and grass) were used, as these should differ significantly in their reactivity towards formaldehyde of their reactive phenolic core units. Additionally a possible influence of the pulping process was addressed by using the different types of lignin from soda, kraft, and organosolv process and various lignosulfonates (sodium, ammonium, calcium, magnesium). To determine the influence of lignin on the adhesive performance beside others the rate of viscosity development, bond strength development of varying hot pressing time and other thermal properties were investigated. To evaluate the performance of the cured end product, a few selected properties were studied at the example of solid wood-adhesive bond joints, compact panels and plywood. As main results it was found that lignin significantly accelerates the viscosity development in adhesive synthesis. Bonding strength development during curing of adhesives decelerated for all lignin types, while this trend was least for pine kraft lignin and spruce sodium lignosulfonate. However, the overall performance of the products prepared with the latter adhesives was able to fulfill main standard requirements, even after exposing the products to harsh environmental conditions. Thus, a potential application can be considered for processes where reactivity is less critical but adhesive cost and product performance is essential.

Keywords: phenol formaldehyde resin, lignin phenol formaldehyde resin, ABES, DSC

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Authors: Kamsiah Jaarin, Yusof Kamisah, Faizah Othman Nurul Akmal Muhammad, Zakiah Jubri, Qodriyah Mohd Saad, Srijit Das

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Forty (40) normotensive adult male Sprague-Dawley rats aged three months weighing 180-200 g were divided into 4 groups with 10 rats per group: (1) normotensive control; (2) hypertensive rats; (3) hypertensive rats treated with Nigella sativa (2.5 ml/kg/day); and (4) hypertensive rats treated with nicardipine (5 mg/kg/day). After acclimatization, the hypertensive rats of the group 2, 3 and 4 were induced to be hypertensive by giving NW–nitro-L-arginine methyl ester (L-NAME; 30 mg/kg/day) in their drinking water for consecutive 7 days. After one week, rats in the group 3 were given a daily oral dose of 2.5 ml/kg/day of Nigella sativa (NS) by oral gavage. Rats in the group 4 were given nicardipine (5 mg/kg/day) via oral gavages. All rats in this study received L-NAME continuously throughout the treatment duration. The blood pressure will be measured pre-treatment and weekly for 8 weeks using power lab. Blood was taken before and at the end of study for measurement of nitric oxide. At the end of 8 weeks, the rats are sacrificed and descending thoracic aorta was disserted for measurement of vascular reactivity, and intracellular adhesion molecules (ICAM-1) and vascular cell adhesion molecules (VCAM-1). Nigella sativa reduced both systolic and diastolic BP compared to control and L-name group. The BP lowering effect of NS was comparable to nicardipine a calcium antagonist. The blood pressure lowering effect of NS was accompanied with an increasing relaxation response to nitroprusside and acetylcholine and reducing vasoconstriction response to epinephrine. L-NAME and nicardipine on the other hand, reduced plasma nitric oxide concentration. In contrast, NS increased NO concentration. However, Nigella sativa had no significant effect on aortic VCAM- 1 and ICAM-1 expression. In conclusion; Nigella sativa oil reduces both systolic and diastolic blood pressure in L-NAME treated rats. The antihypertensive effect of NS was comparable to nicardipine. The BP lowering effect may be mediated via stimulating nitric oxide release from vascular endothelium.

Keywords: Nigella sativa, ICAM, VCAM, blood pressure, vascular reactivity

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Authors: Christian Uchechukwu Gilbert

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Generativism in language design investigates the framework on which varying sentence structures are built in the English language. Propounded by Noam Chomsky in 1965, the theory transforms sentences from an active structure to a passive one by the application of established rules of the theory. Resident in the body of syntax, the rules include movement, insertion, substitution, and deletion rules. Using the movement rule, the analysis is armed with the qualitative research method, on which the works of scholars were duly consulted for more insight and in line with the academic practice in research activities. The investigation showed that the rules of competent grammar explain the formulation of sentences in a language and how transformation takes place among sentences from a deep structure to a surface structure with accurate results. The structural differences that could be got through dative movement and the deletion of the preposition; passivisation got from an active sentence by the insertion of the preposition “by” a “be verb” and the aspect tense marker “–en”, held as the creative aspect of language vocabulary and the subject-auxiliary inversion that exchanges the auxiliary of a sentence with the subject of the same sentence thereby transforming a kennel sentence to a polar question, viewed as an external argument under θ-theory. Generativism in language design, therefore, changes available types of sentences and relates one form of linguistic category with others in language design.

Keywords: language, generate, transformation, structure, design

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Authors: M. Srilatha, R. Hemalatha, T. Sri Aditya

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Communication of today world is dominated by wireless technology. This is mainly due to the revolutionary development of new wireless communication system generations. The evolving new generations of wireless systems are accommodating the demand through better resource management including improved transmission technologies with optimized communication devices. To keep up with the evolution of technologies, the communication systems must be designed to optimize transparent insertion of newly evolved technologies virtually at all stages of their life cycle. After the insertion of new technologies, the upgraded devices should continue the communication without squalor in quality. The concern of improving spectrum access and spectrum efficiency combined with both the introduction of Software Defined Radios (SDR) and the possibility of the software application to radios has led to an evolution of wireless radio research. The software defined radio term was coined in the 1970s to overcome the problems in the application of software to wireless radios which eliminates the requirement of hardware changes. SDR has become the prime theme of research since it eliminates the drawbacks associated with conventional wireless communication systems implementation. This paper identifies and discusses key enabling technologies and possibility of research and development in SDRs. In addition transmitter and receiver architectures of SDR are also discussed along with their feasibility for reconfigurable radio application.

Keywords: software defined radios, wireless communication, reconfigurable, reconfigurable transmitter, reconfigurable receivers, FPGA, DSP

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Authors: M'Hamed Boulakroune, Mouloud Challal, Hassiba Louazene, Saida Fentiz

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This paper presents a new ultra wideband (UWB) microstrip bandpass filter (BPF) at microwave frequencies. The first one is based on multiple-mode resonator (MMR) and rectangular-shaped defected ground structure (DGS). This filter, which is compact size of 25.2 x 3.8 mm2, provides in the pass band an insertion loss of 0.57 dB and a return loss greater than 12 dB. The second structure is a tunable bandpass filters using planar patch resonators based on diode varactor. This filter is formed by a triple mode circular patch resonator with two pairs of slots, in which the varactors are connected. Indeed, this filter is initially centered at 2.4 GHz, the center frequency of the tunable patch filter could be tuned up to 1.8 GHz simultaneously with the bandwidth, reaching high tuning ranges. Lossless simulations were compared to those considering the substrate dielectric, conductor losses, and the equivalent electrical circuit model of the tuning element in order to assess their effects. Within these variations, simulation results showed insertion loss better than 2 dB and return loss better than 10 dB over the passband. The proposed filters presents good performances and the simulation results are in satisfactory agreement with the experimentation ones reported elsewhere.

Keywords: defected ground structure, diode varactor, microstrip bandpass filter, multiple-mode resonator

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Authors: Soraya Abtouche, Zeyneb Ghoualem, Syrine Daoudi, Lina Ouldmohamed, Xavier Assfeld

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This work reports density functional theory calculations of the optimized geometries, molecular reactivity, energy gap,and thermodynamic properties of the free base (H2P) and their Zn (II) metallated (ZnP), bearing one, two, or three carboxylic acid groups using the hybrid functional B3LYP, Cam-B3lYP, wb97xd with 6-31G(d,p) basis sets. When donating groups are attached to the molecular dye, the bond lengths are slightly decreased, which is important for the easy transfer of an electron from donating to the accepting group. For all dyes, the highest occupied molecular orbital/lowest occupied molecular orbital analysis results in positive outcomes upon electron injection to the semiconductor and subsequent dye regeneration by the electrolyte. The ionization potential increases with increasing conjugation; therefore, the compound dye attached to one carboxylic acid group has the highest ionization potential. The results show higher efficiencies of those sensitized with ZnP. These results have been explained, taking into account the electronic character of the metal ion, which acts as a mediator in the injection step, and, on the other hand, considering the number of anchoring groups to which it binds to the surface of TiO2.

Keywords: DSSC, porphyrin, TD-DFT, electronic properties, donor-acceptor groups

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Authors: Despina Vamvuka, Despina Pentari

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Forestry wastes are readily available in large quantities around the world. Based on European Green Deal for the deployment of renewable and decarbonized energy by 2050, as well as global energy crisis, energy recovery from such wastes reducing greenhouse gas emissions is very attractive. Gasification has superior environmental performance to combustion, producing a clean fuel gas utilized in internal combustion engines, gas turbines, solid oxide fuel cells, or for synthesis of liquid bio-fuels and value-added chemicals. In this work, pine needles, which are abundantly found in Mediterranean countries, were gasified by either steam or carbon dioxide via a two-step process to improve reactivity and eliminate tar, employing a fixed bed unit and a thermal analysis system. Solid, liquid and gaseous products from the whole process were characterized and their energy potential was determined. Thermal behaviour, reactivity, conversion and energy recovery were examined. The gasification process took place above 650°C. At 950°C conversion and energy recovery were 77% dry and 2 under a flow of steam and 85% dry and 2.9 under a flow of carbon dioxide, respectively. Organic matter was almost completely converted to syngas, the yield of which varied between 89% and 99%. The higher heating values of biochar, bio-oil and pyrolysis gas were 27.8 MJ/kg, 33.5 MJ/kg and 13.6 MJ/m3. Upon steam or carbon dioxide gasification, the higher heating value of syngas produced was 11.5 MJ/m3 and 12.7 MJ/m3, respectively.

Keywords: gasification, biomass, steam, carbon dioxide

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Authors: Kulsum Maula, Md Kamrul Alam, Md Ibrahim Khalil, Md Nazmul Hasan, Mohammad Omar Faruq

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Background: Percutaneous Tube Thoracostomy (PTT) is an invasive procedure that can save a life now and then in different traumatic and non-traumatic conditions. But still, it is an enigma; how our trainee surgeons are at home in this procedure. Objectives: To evaluate the outcome of the percutaneous tube thoracostomy performed by trainees in both trauma and non-trauma patients. Study design: Prospective, Observational Study. The duration of the study was September 2018 to February 2019. Methods: All patients who need PTT in traumatic and non-traumatic conditions were selected by purposive sampling. Thereafter, they were scrutinized according to eligibility criteria and 96 patients were finalized. A pre-tested, observation-based, peer-reviewed data collection sheet was prepared before the study. Data regarding clinical and surgical outcome profiles were recorded. Data were compiled, edited, and analyzed. Results: Among 96 patients, the highest 32.29% belonged to age group 31-40 years and the lowest 9.37% belonged to the age group ≤20. The mean age of the respondents was 29.19±9.81. We found out of 96 patients, 70(72.91%) were indicated PTT for traumatic conditions and the rest 26(27.08%) were indicated PTT for non-traumatic chest conditions, where 36(37.5%) had simple penumothorax, 21(21.87%) haemothorax, 14(14.58%) massive pleural effusion, 13(13.54%) tension pneumothorax, 10(10.41%) haemopneumothorax, and 2(2.08%) had pyothorax respectively. In 53.12% of patients had right-sided intercostal chest tube (ICT) insertion, whereas 46.87% had left-sided ICT insertion. In our study, 89.55 % of the tube was placed at the normal anatomical position. Besides, 10.41% of tube thoracostomy were performed deviated from anatomical site. Among 96 patients 62.5% patients had length of incision 2-3cm, 35.41% had >3cm and 2.08% had <2cm respectively. Out of 96 patients, 75(78.13%) showed uneventful outcomes, whereas 21(21.87%) had complications, including 11.15%(11) each had wound infection, 4.46%(4) subcutaneous emphysema, 4.28%(3) drain auto expulsion, 2.85%(2) hemorrhage, 1.45%(1) had a non-functioning drain and empyema with ascending infection respectively (p=<0.05). Conclusion: PTT is a life-saving procedure that is most frequently implemented in chest trauma patients in our country. In the majority of cases, the outcome of PTT was uneventful (78.13). Besides this, more than one-third of patients had a length of incision more than 3 cm that needed extra stitches and 10.41% of cases of PTT were placed other than the normal anatomical site. Trainees of Dhaka Medical College Hospitals are doing well in their performance of PTT insertion, but still, some anatomical orientations are necessary to avoid operative and post-operative complications.

Keywords: PTT, trainee, trauma, non-chest trauma patients

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Authors: Hiroshi Kinoshita, Yasuto Nakanishi, Ryuhei Okuno, Toshio Higashi

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Various kinds of pegboards have been developed and used widely in research and clinics of rehabilitation for evaluation and training of patient’s hand function. A common measure in these peg boards is a total time of performance execution assessed by a tester’s stopwatch. Introduction of electrical and automatic measurement technology to the apparatus, on the other hand, has been delayed. The present work introduces the development of a pegboard with an electric sensor to detect moments of individual peg’s insertion and removal. The work also gives fundamental data obtained from a group of healthy young individuals who performed peg transfer tasks using the pegboard developed. Through trails and errors in pilot tests, two 10-hole peg-board boxes installed with a small photo-reflector and a DC amplifier at the bottom of each hole were designed and built by the present authors. The amplified electric analogue signals from the 20 reflectors were automatically digitized at 500 Hz per channel, and stored in a PC. The boxes were set on a test table at different distances (25, 50, 75, and 125 mm) in parallel to examine the effect of hole-to-hole distance. Fifty healthy young volunteers (25 in each gender) as subjects of the study performed successive fast 80 time peg transfers at each distance using their dominant and non-dominant hands. The data gathered showed a clear-cut light interruption/continuation moment by the pegs, allowing accurately (no tester’s error involved) and precisely (an order of milliseconds) to determine the pull out and insertion times of each peg. This further permitted computation of individual peg movement duration (PMD: from peg-lift-off to insertion) apart from hand reaching duration (HRD: from peg insertion to lift-off). An accidental drop of a peg led to an exceptionally long ( < mean + 3 SD) PMD, which was readily detected from an examination of data distribution. The PMD data were commonly right-skewed, suggesting that the median can be a better estimate of individual PMD than the mean. Repeated measures ANOVA using the median values revealed significant hole-to-hole distance, and hand dominance effects, suggesting that these need to be fixed in the accurate evaluation of PMD. The gender effect was non-significant. Performance consistency was also evaluated by the use of quartile variation coefficient values, which revealed no gender, hole-to-hole, and hand dominance effects. The measurement reliability was further examined using interclass correlation obtained from 14 subjects who performed the 25 and 125 mm hole distance tasks at two 7-10 days separate test sessions. Inter-class correlation values between the two tests showed fair reliability for PMD (0.65-0.75), and for HRD (0.77-0.94). We concluded that a sensor peg board developed in the present study could provide accurate (excluding tester’s errors), and precise (at a millisecond rate) time information of peg movement separated from that used for hand movement. It could also easily detect and automatically exclude erroneous execution data from his/her standard data. These would lead to a better evaluation of hand dexterity function compared to the widely used conventional used peg boards.

Keywords: hand, dexterity test, peg movement time, performance consistency

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Authors: Hendrik Bernard Van Der Walt, Frik Van Niekerk

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Fuel models render a reduction in BOL when thorium is added to a reactor core. Thorium emulates the role of a fertile poison, and is beneficial for reducing beginning of cycle (BOC) excess reactivity. In spite of the build-up of 233U over the duration of a fuel cycle, the effects of fuel reloading have a significant impact on fuel viability, especially in the case of heterogeneous thorium-based fuels. The most common practice of compensating for the reduction of BOC reactivity is the addition of fissile isotopes (uranium fuel with increased enrichment or plutonium). This study introduces a heterogeneous thorium-based fuel with minimal fissile isotope additions. A pseudo reloading scheme was developed for numerical simulations of an infinite reactor based on the North-Anna 1 reactor operating in Virginia, USA. Use of this reloading pattern allows new thorium-based fuel to be loaded into the reactor model as part of a phasing in strategy at the end of any conventional reactor cycle. Results demonstrate the effects of thorium-based fuel on fuel cycle characteristics such as fuel cycle length, neutron economy and material matrix. Application of the above mentioned approach delivered promising results and presents a heterogeneous thorium-based fuel which could replace conventional fuel of typical, currently operating (or future) reactors without the need for expensive reactor redesign or fuel recycling strategies.

Keywords: nuclear fuel, nuclear characteristics, nuclear fuel cycle, thorium-based fuel, heterogeneous design, fuel reloading

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Authors: Ana Paula Melchiors Stahlschmidt

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This paper discusses the role of music as a ludic activity and constituent element of voice in the construction and consolidation of the relationship of the baby and his/her mother or caretaker, evaluating its implications in his/her psychic structure and constitution as a subject. The work was based on the research developed as part of the author’s doctoral activities carried out from her insertion in a project of the Music Department of Federal University of Rio Grande do Sul - UFRGS, which objective was the development of musical activities with groups of babies from 0 to 24 months old and their caretakers. Observations, video recordings of the meetings, audio testemonies, and evaluation tools applied to group participants were used as instruments for this research. Information was collected on the participation of 195 babies, among which 8 were more focused on through interviews with their mothers or caretakers. These interviews were analyzed based on the referential of French Discourse Analysis, Psychoanalysis, Psychology of Development and Musical Education. The results of the research were complemented by other posterior experiences that the author developed with similar groups, in a context of a private clinic. The information collected allowed the observation of the ludic and structural functions of musical activities, when developed in a structured environment, as well as the importance of the musicality of the mother’s voice to the psychical structuring of the baby, allowing his/her insertion in the language and his/her constituition as a subject.

Keywords: music and babies, maternal voice, Psychoanalysis and music, psychology and music

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Authors: Adrien Cornille, Marine Blain, Bernard Boutevin, Sylvain Caillol

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Generally, linear polyurethanes (PUs) are obtained by the reaction between an oligomeric diol, a short diol as chain extender and a diisocyanate. However the use of diisocyanate should be avoided since they are generally very harmful for human health. Therefore the synthesis of NIPUs (non isocyanate PUs) from step growth polymerization of dicyclocarbonates and diamines should be favoured. This method is particularly interesting since no hazardous isocyanates are used. Thus, this reaction, extensively studied by Endo et al. is currently gaining a lot of attention as a substitution route for the synthesis of NIPUs, both from industrial and academic community. However, the reactivity of reaction between amine and cyclic carbonate is a major scientific issue, since cyclic carbonates are poorly reactive. Thus, our team developed several synthetic ways for the synthesis of various di-cyclic carbonates based on C5-, C6- and dithio- cyclic carbonates, from different biobased raw materials (glycerin isosorbide, vegetable oils…). These monomers were used to synthesize NIPUs with various mechanical and thermal properties for various applications. We studied the reactivity of reaction with various catalysts and find optimized conditions for room temperature reaction. We also studied the radical copolymerization of cyclic carbonate monomers in styrene-acrylate copolymers for coating applications. We also succeeded in the elaboration of biobased NIPU flexible foams. To the best of our knowledge, there is no report in literature on the preparation of non-isocyanate polyurethane foams.

Keywords: foam, nonisocyanate polyurethane, cyclic carbonate, blowing agent, scanning electron microscopy

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Authors: Karlee J. Hall, Mark Laylor, Jessy Varghese, Paula Polastri, Karen Van Ooteghem, William McIlroy

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Balance training is a common part of physiotherapy treatment and often involves a set of proprioceptive exercises which the patient carries out in the clinic and as part of their exercise program. Understanding all contributing factors to altered balance is of utmost importance to the clinical success of treatment of balance dysfunctions. A critical role for the autonomic nervous system (ANS) in the control of balance reactions has been proposed previously, with evidence for potential involvement being inferred from the observation of phasic galvanic skin responses (GSR) evoked by external balance perturbations. The current study explored whether the coupling between ANS reactivity and balance reactions would be observed during spontaneously occurring instability while standing, including standard positions typical of physiotherapy balance assessments. It was hypothesized that time-varying changes in GSR (ANS reactivity) would be associated with time-varying changes in the mediolateral center of pressure (ML-COP) (somatomotor reactivity). Nine individuals (5 females, 4 males, aged 19-37 years) were recruited. To induce varying balance demands during standing, the study compared ML-COP and GSR data across different task conditions varying the availability of vision and width of the base of support. Subjects completed 3, 30-second trials for each of the following stance conditions: standard, narrow, and tandem eyes closed, tandem eyes open, tandem eyes open with dome to shield visual input, and restricted peripheral visual field. ANS activity was evaluated by measures of GSR recorded from Ag-AgCl electrodes on the middle phalanges of digits 2 and 4 on the left hand; balance measures include ML-COP excursion frequency and amplitude recorded from two force plates embedded in the floor underneath each foot. Subjects were instructed to stand as still as possible with arms crossed in front of their chest. When comparing mean task differences across subjects, there was an expected increase in postural sway from tasks with a wide stance and no sensory restrictions (least challenging) to those with a narrow stance and no vision (most challenging). The correlation analysis revealed a significant positive relationship between ML-COP variability and GSR variability when comparing across tasks (r=0.94, df=5, p < 0.05). In addition, correlations coincided within each subject and revealed a significant positive correlation in 7 participants (r= 0.47, 0.57, 0.62, 0.62, 0.81, 0.64, 0.69 respectively, df=19, p < 0.05) and no significant relationship in 2 participants (r=0.36, 0.29 respectively, df=19, p > 0.05). The current study revealed a significant relationship between ML-COP and GSR during balance tasks, revealing the ANS reactivity associated with naturally occurring instability when standing still, which is proportional to the degree of instability. Understanding the link between ANS activity and control of COP is an important step forward in the enhancement of assessment of contributing factors to poor balance and treatment of balance dysfunctions. The next steps will explore the temporal association between the time-varying changes in COP and GSR to establish if the ANS reactivity phase leads or lags the evoked motor reactions, as well as exploration of potential biomarkers for use in screening of ANS activity as a contributing factor to altered balance control clinically.

Keywords: autonomic nervous system, balance control, center of pressure, somatic nervous system

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Authors: Jaime R. Silva, Gabriel E. Reyes, Marianne Krause

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Background: The two-polarity model of the depressive personality argues that experience is organized around two axes: interpersonal relatedness and self-definition. Differential emphasis on one of these poles defines three types of depressive experience: Anaclitic, Introjective or Mixed pattern. On the one hand, Anaclitic pattern has been conceptually related with exaggerated biological stress sensitivity. On the other hand, the Introjective pattern was linked with anhedonic symptomatology. The general aim of the study was to find empirical support for this relationship. Methods: 101 non-clinical individuals participated in two experimental sessions. During the first session, the biological stress reactivity (cortisol concentration in saliva) and the subjective stress perceived (self-reported) during the Trier Social Stress Test (TSST), were investigated. In the second session, a visual discrimination task with a specific reward system, to study the reinforcement sensitivity (anhedonia), was performed. Results: Results evidenced that participants with Introjective depressive symptoms showed a higher interpersonal sensitivity and a diminished sensitivity to reinforcement. In addition, results also indicated that such a group has a poor psychological detection of its exacerbated reactivity to stress, which is the opposite pattern evidenced amongst the Anaclitic group. Conclusions: In perspective, these results empirically support the two-polarity of the depressive personality model. Clinical implications are discussed.

Keywords: depression, interpersonal stress, personality, trier social stress test

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Authors: Schirin Hanf, Carlos Lizandara-Pueyo, Timmo P. Emmert, Ivana Jevtovikj, Roger Gläser, Stephan A. Schunk

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Metal alkoxides are very versatile precursors for a broad array of complex functional materials. However, metal alkoxides, especially transition metal alkoxides, tend to form oligomeric structures due to the very strong M–O–M binding motif. This fact hinders their facile application in sol-gel-processes and complicates access to complex carbonate or oxidic compounds after hydrolysis of the precursors. Therefore, the development of a synthetic alternative with the aim to grant access to carbonates and hydroxycarbonates from simple metal alkoxide precursors via hydrolysis is key to this project. Our approach involves the reaction of metal alkoxides with unsaturated isoelectronic molecules, such as carbon dioxide. Subsequently, a stoichiometric insertion of the CO₂ into the alkoxide M–O bond takes place and leads to the formation of soluble metal alkyl carbonates. This strategy is a very elegant approach to solubilize metal alkoxide precursors to make them accessible for sol-gel chemistry. After hydrolysis of the metal alkyl carbonates, crystalline metal carbonates, and hydroxycarbonates can be obtained, which were then utilized for the synthesis of Cu/Zn based bulk catalysts for methanol synthesis. Using these catalysts, a comparable catalytic activity to commercially available MeOH catalysts could be reached. Based on these results, a complement for traditional precipitation techniques, which are usually utilized for the synthesis of bulk methanol catalysts, have been found based on an alternative solubilization strategy.

Keywords: metal alkoxides, metal carbonates, metal hydroxycarbonates, CO₂ insertion, solubilization

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Authors: Srinivasapriyan Vijayan

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Phenol is one of the most vital chemical in industry. Nowadays, phenol production is based upon the three-step cumene process, which involves a hazardous cumene hydroperoxide intermediate and produces nearly equimolar amounts of acetone as a coproduct. An attractive route in phenol production is the direct one-step selective hydroxylation of benzene using eco-friendly oxidants such as O2, N2O, and H2O2. In particular, the direct hydroxylation of benzene to form phenol with O2 has recently attracted extensive research attention because this process is green clean and eco-friendly. However, most of the catalytic systems involving O2 have a low rate of hydroxylation because the direct introduction of hydroxyl functionality into benzene is challenging. Almost all the developed catalytic systems require an elevated temperature and suffer from low conversion because of the notoriously low reactivity of aromatic C–H bonds. Moreover, increased reactivity of phenol relative to benzene makes the selective oxidation of benzene to phenol very difficult, especially under heating conditions. Hollow spheres, a very fascinating class of materials with good permeation and low density, highly monodisperse MOF hollow sandwich spheres have been rationally synthesized using monodisperse polystyrene (PS) nanoparticles as templates through a versatile step-by-step self-assembly strategy. So, our findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis. Because it is easy post-reaction separation, its cheap, green and recyclable.

Keywords: benzene hydroxylation, Fe-based metal organic frameworks, molecular oxygen, phenol

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