scholarly journals Perturbed and Unperturbed: Analyzing the Conservatively Perturbed Equilibrium (Linear Case)

Entropy ◽  
2020 ◽  
Vol 22 (10) ◽  
pp. 1160
Author(s):  
Yiming Xi ◽  
Xinquan Liu ◽  
Denis Constales ◽  
Gregory S. Yablonsky

The “conservatively perturbed equilibrium” (CPE) technique for a complex chemical system is computationally analyzed in a batch reactor considering different linear mechanisms with three and four species. Contrary to traditional chemical relaxation procedures, in CPE experiments only some initial concentrations are modified; other conditions, including the total amount of chemical elements and temperature are kept unchanged. Generally, for “unperturbed” species with initial concentrations equal to their corresponding equilibrium concentrations, unavoidable extreme values are observed during relaxation to the equilibrium. If the unperturbed species is involved in one step only, this extremum is a momentary equilibrium of the step; if the unperturbed species is involved in more reactions, the extremum is not a momentary equilibrium. The acyclic mechanism with four species may exhibit two extrema and an inflection point, which corresponds to an extremum of the rate of the species change. These facts provide essential information about the detailed mechanism of the complex reaction.

2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>


2018 ◽  
Vol 1 (1) ◽  
pp. 1 ◽  
Author(s):  
Bernd Markert ◽  
Simone Wünschmann ◽  
Jörg Rinklebe ◽  
Stefan Fränzle ◽  
Tarek Ammari

Background: In order to account for the physiological effects of chemical elements in living organisms using some Biological System of Elements (BSE) established by Markert in 1994 [1], the familiar Periodic Chemical System of Elements (PSE) according to Mendelejew and Meyer from 1869 was completed and modified using the Geochemical System of Elements (GSE) by Railsback [2-4, 5]. BSE goes beyond accumulating essentiality investigations, despite obvious technical and analytical limitations. In correlation among abundances of elements in different samples of biological origins, there are deep-rooted biochemical factors and relationships which these authors began studying and describing in more detail in the late 1990´s. Until the end of 2017, the BSCE was referred to as the Biological System of Elements (BSE).Lithium is not considered a vital or essential trace element. However, lithium is present in our body and has important functions, especially for the psyche. Specifically, lithium is important for mental health. The application of Li as pharmaceutical therapeutic equivalent for bipolar disorders (formerly called manic depressive disorders) is a well-known example of the use of a monovalent cation on neurological therapy. One of the main scientific objectives of this review and future research is the use of functional food in supporting and balancing the therapeutic dose of Li in the human body. In order to describe a possible application of a "functional food therapy by Li” and to meet its “scientific philosophy" a first look was given to Li-accumulating plants. We explain the use of plants containing high amounts of Li and described possible effects of increased Li concentrations in the human body.Finally, we should confirm if "natural food therapy” (for instance “green pills”) can positively support mental human health care benefits by fitting the ratio of Li / neurological diseases. For example, diseases like chronic bipolar disorders. Accordingly, the BSCE will continue to identify and investigate other chemical elements for using them in an effective Functional Food Therapy (FFT) of chronic neurological diseases and possibly other diseases. Keywords: Biological System of Chemical Elements (BSCE), Lithium (Li), Bipolar Disorders, Neurology, Functional Food Therapy (FFT), Chronic diseases 


2019 ◽  
Vol 9 (3) ◽  
pp. 418 ◽  
Author(s):  
Young-Ik Choi ◽  
Hyeon-Jo Ji ◽  
Dae-Yeol Shin ◽  
Sana Mansoor ◽  
Min-Ji Kwan ◽  
...  

International Maritime Organization recognizes vessel-induced pollution as a global issue. The designation of the Baltic Sea as the special uncontaminated area was the beginning of the regulations for preventing marine pollution. In this regard, a process is needed which meets the provisions of MEPC. 227(64) for the specificity and constrained conditions of vessels, removes both nitrogen and phosphorus, requires convenient operation and low construction cost and is little affected by the load variation of inflow. This study used an SBR(sequencing batch reactor) and MBR(membrane bioreactor) combined process to iterate the stirring and aeration process and maintained the ratio of raw wastewater parameters (C:N:P) to be 10:3:1 in order to assess the quality and future availability of ultimate outflow in each time period of the stirring and aeration process. The removal efficiencies of COD and T-N exceeded 90% and 93% respectively. However, a detailed mechanism will be identified by a further study on nitrogen removal issues like DO aeration condition, stirring duration, ORP and NO3. As the removal efficiency of T-P exceeded 95%, the SBR and MBR process formed anaerobic and aerobic conditions without a separate coagulation process for removing phosphorus, thereby enabling easy phosphorus release and uptake. The optimal stirring and aeration condition seems to be 70–50 min. A further study will be efficiently conducted by focusing on the water quality criteria of the Maritime Environment Protect Committee. 227 (64) for E. coli and chlorine and a detailed mechanism.


2019 ◽  
Author(s):  
Mark Workentin ◽  
François Lagugné-Labarthet ◽  
Sidney Legge

In this work we present a clean one-step process for modifying headgroups of self-assembled monolayers (SAMs) on gold using photo-enabled click chemistry. A thiolated, cyclopropenone-caged strained alkyne precursor was first functionalized onto a flat gold substrate through self-assembly. Exposure of the cyclopropenone SAM to UV-A light initiated the efficient photochemical decarbonylation of the cyclopropenone moiety, revealing the strained alkyne capable of undergoing the interfacial strain-promoted alkyne-azide cycloaddition (SPAAC). Irradiated SAMs were derivatized with a series of model azides with varied hydrophobicity to demonstrate the generality of this chemical system for the modification and fine-tuning of the surface chemistry on gold substrates. SAMs were characterized at each step with polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) to confirm successful functionalization and reactivity. Furthermore, to showcase the compatibility of this approach with biochemical applications, cyclopropenone SAMs were irradiated and modified with azide-bearing cell adhesion peptides to promote human fibroblast cell adhesion, then imaged by live cell fluorescence microscopy. Thus, the “photoclick” methodology reported here represents an improved, versatile, catalyst-free protocol that allows for a high degree of control over the modification of material surfaces, with applicability in materials science as well as biochemistry.<br>


Author(s):  
Owen M. Pryor ◽  
Subith Vasu ◽  
Xijia Lu ◽  
David Freed ◽  
Brock Forrest

There has been some recent work on the global kinetic modeling of flames in oxy-fuel combustion for methane. The main challenge is that none of the mechanisms were developed to understand the time-scales of ignition. Here, a 3-step mechanism was developed for methane combustion in oxy-fuel environment. The mechanisms were simulated using a closed batch homogeneous batch reactor with constant pressure and compared to baseline simulations performed using a detailed mechanism. All simulations were performed for methane used a mixture of XCH4 = 0.05, XO2 = 0.10 and XCO2 = 0.85. Mechanisms were altered using the global mechanism equilibrium approach to ensure that the steady-state values matched the reference values and were further altered using an optimization scheme to match experimental data that was taken in a shock tube. Simulation results of methane, CO time-histories, and temperature profiles from the global mechanism were compared to those from the detailed mechanism. Ignition delay times were used to represent the time-scales of combustion. This was defined for current simulations as the time required for methane concentration to reach 5% of its initial value during combustion. Using this approach, the 3-step methane combustion mechanism showed excellent improvement in the ignition timing over a range of pressures (1 to 10 bar) and initial temperatures (1500 to 2000 K) for both lean and stoichiometric mixtures but fails to predict ignition delay times at 30 bar or the ignition delay times of fuel rich mixtures. Ongoing effort focuses on extending this new global mechanism to higher pressures and to syngas mixtures.


2014 ◽  
Vol 1070-1072 ◽  
pp. 152-156
Author(s):  
Yong Yan Zhao ◽  
Yu Bao Chen ◽  
Shun Ping Yang ◽  
Wu Di Zhang ◽  
Yan Ni Gao

One-step hydrotreatment of three different vegetable oils have been carried out over Pd loading bi-functional catalyst in batch reactor. Rubber seed oil, Jatropha oil and castor oil have different acid value and constituents, which will influence the hydroprocessing and the quality of products. With temperature rising, several principles have been summarized, and an optimal temperature corresponding to three oils have been determined respectively. At the optimal temperature of Jatropha oil, 300°C, deoxygenation rate was up to 99.29%, C8-16hydrocarbons of products was up to 77.36%; 310°C and 320°C were respectively optimal temperature of rubber seed oil and castor oil, deoxygenation rate were 99.15% and 98.78%, C8-16hydrocarbons were 71.46% and 69.25%. The products quality of Jatropha oil was better than rubber seed oil and castor oil, and rubber seed oil and castor oil can cause the deactivation of catalyst.


Author(s):  
Naga Narendra B. Bodapati ◽  
Robert J. Peterman ◽  
B. Terry Beck ◽  
Chih-Hang John Wu

This paper presents findings from a current research project titled “Quantifying the Effect of Prestressing Steel and Concrete Variables on the Transfer Length in Pretensioned Concrete Crossties” that is funded by the Federal Railroad Administration (FRA). Specifically, the paper focuses on the effect of concrete properties on the resulting transfer lengths. These properties include concrete consistency (slump), compressive strength at the time of prestress transfer, the water-to-cementitious (W/C) ratio, the aggregate type, and the use of a viscosity-modifying admixture (VMA). Pre-tensioned concrete prisms were cast in the laboratory and transfer lengths were determined from surface strain measurements that were obtained prior-to and immediately after prestress transfer (de-tensioning). The concrete compressive strength at de-tensioning was determined using cylindrical concrete test specimens that were match-cured to the temperature of the pre-tensioned concrete members. The release strengths investigated were 3500 psi (24.13 Mpa), 4500 psi (31.03 Mpa), and 6000 psi (41.37 Mpa). The effect of concrete consistency on the transfer length was evaluated by varying the slump between 3″ (76.20 mm) and 9″ (228.60 mm) while maintaining release strength of 4500 psi (31.03 Mpa) and a W/C ratio of 0.32. The effect of W/C ratio on transfer length was evaluated by maintaining release strength of 4500 ±220 psi (31.03 ± 1.52 Mpa) and a slump of 6 ± 1/2″ (152.40 ± 12.7 mm) while varying the W/C between 0.27 and 0.42. These values represent the extreme values used in the North American concrete tie industry that were noted by the authors during research that was conducted in 2010–2011[15]. Results for each parameter type will be compared and discussed in this paper. Transfer length results obtained during earlier work [4] conducted by the authors at a W/C ratio of 0.32 will be compared. Finally, results will be presented from transfer length measurements that were obtained on identical-sized prisms that were manufactured with concrete mixtures that used different aggregate sources and also the use of a viscosity-modifying admixture. Work presented in this paper was conducted on two wire samples with generic labels [WG] and [WH]. Laboratory prism specimens of size 3 ½″ (88.9 mm) × 3 ½″ (88.9 mm) each with 4 wires were cast to measure transfer lengths. These proportions were chosen to replicate the original concrete crosstie wire-to-concrete proportions. Potential usage of these prisms in estimating transfer lengths was validated in another phase [5] and is not discussed here. Essential information obtained from results allowed researchers to discuss attributed influence of each concrete property on transfer length. The research knowledge acquired from this study will give proper insight about transfer length and will be helpful to manufacture a better product by adjusting concrete mix design.


Author(s):  
J. Jaime Gómez-Hernández ◽  
R. Mohan Srivastava

AbstractIn the mid-1980s, still in his young 40s, André Journel was already recognized as one of the giants of geostatistics. Many of the contributions from his new research program at Stanford University had centered around the indicator methods that he developed: indicator kriging and multiple indicator kriging. But when his second crop of graduate students arrived at Stanford, indicator methods still lacked an approach to conditional simulation that was not tainted by what André called the ‘Gaussian disease’; early indicator simulations went through the tortuous path of converting all indicators to Gaussian variables, running a turning bands simulation, and truncating the resulting multi-Gaussian realizations. When he conceived of sequential indicator simulation (SIS), even André likely did not recognize the generality of an approach to simulation that tackled the simulation task one step at a time. The early enthusiasm for SIS was its ability, in its multiple-indicator form, to cure the Gaussian disease and to build realizations in which spatial continuity did not deteriorate in the extreme values. Much of Stanford’s work in the 1980s focused on petroleum geostatistics, where extreme values (the high-permeability fracture zones and the low-permeability shale barriers) have much stronger anisotropy, and much longer ranges of correlation in the maximum continuity direction, than mid-range values. With multi-Gaussian simulations necessarily imparting weaker continuity to the extremes, SIS was an important breakthrough. The generality of the sequential approach was soon recognized, first through its analogy with multi-variate unconditional simulation achieved using the lower triangular matrix of an LU decomposition of the covariance matrix as the multiplier of random normal deviates. Modifying LU simulation so that it became conditional gave rise to sequential Gaussian simulation (SGS), an algorithm that shared much in common with SIS. With nagging implementation details like the sequential path and the search neighborhood being common to both methods, improvements in either SIS or SGS often became improvements to the other. Almost half of the contributors to this Special Issue became students of André in the classes of 1984–1988, and several are the pioneers of SIS and SGS. Others who studied later with André explored and developed the first multipoint statistics simulation procedures, which are based on the same concept that underlies sequential simulation. Among his many significant intellectual accomplishments, one of the cornerstones of André Journel’s legacy was sequential simulation, built one step at a time.


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