scholarly journals Predicting Partition Coefficients of Short-Chain Chlorinated Paraffin Congeners by COSMO-RS-Trained Fragment Contribution Models

Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work uses a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C<sub>4</sub> in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors. The FCM predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.<br>

2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work uses a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C<sub>4</sub> in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors. The FCM predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.<br>


2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work combines a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to establish models to predict partition coefficients of a large number of short-chain chlorinated paraffin (SCCP) congeners. Molecular fragments of a length of up to C<sub>4</sub> in CP molecules were counted and used as explanatory variables to develop linear regression models for predicting COSMO-RS-calculated values. The resulting models can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors (RMSE). The model predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The ranges of partition coefficients for each SCCP congener group were computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed approach, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.


2020 ◽  
Author(s):  
Satoshi Endo ◽  
Jort Hammer

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated <i>n</i>-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work combines a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to establish models to predict partition coefficients of a large number of short-chain chlorinated paraffin (SCCP) congeners. Molecular fragments of a length of up to C<sub>4</sub> in CP molecules were counted and used as explanatory variables to develop linear regression models for predicting COSMO-RS-calculated values. The resulting models can quickly provide COSMO-RS predictions for octanol–water (<i>K</i><sub>ow</sub>), air–water (<i>K</i><sub>aw</sub>), and octanol–air (<i>K</i><sub>oa</sub>) partition coefficients of SCCP congeners with an accuracy of 0.1–0.3 log units root mean squared errors (RMSE). The model predictions for <i>K</i><sub>ow</sub> agree with experimental values for individual constitutional isomers within 1 log unit. The ranges of partition coefficients for each SCCP congener group were computed, which successfully reproduced experimental log <i>K</i><sub>ow</sub> ranges of industrial CP mixtures. As an application of the developed approach, the predicted <i>K</i><sub>aw</sub> and <i>K</i><sub>oa</sub> were plotted to evaluate the bioaccumulation potential of each SCCP congener group.


1977 ◽  
Vol 55 (12) ◽  
pp. 2404-2410 ◽  
Author(s):  
Douglas M. Chen ◽  
Fred Y. Fujiwara ◽  
Leonard W. Reeves

The degree of order of solubilized molecules and ions in oriented lyomesophases has been determined at specifically deuterated C—D bond axes from the quadrupole splitting of the deuterium magnetic resonance. Mixtures at low concentration of specifically deuterated alkanes, alcohols, carboxylic acids, and carboxylates of different chain length have been observed in host cationic and anionic lyomesophases. The degree of order of a given C—D position in alcohols increases strongly with chain length up to a length comparable with the host detergent. A broad series of carboxylic acids and carboxylate ions from C2 to C16 have been deuterated in the α position. The α-C—D bond axis in the solubilisate increases in order with chain length, the anion having lower order than the parent acid. An accurately linear increase in the degree of order of the α position is observed for intermediate chain lengths. At chain lengths approximately equal to the host chain lengths the α position reaches a limiting value in the degree of order and further segments do not influence the order. At short chain lengths the degree of order is less than that predicted from extrapolation of order in the linear region. This has been interpreted in terms of distribution into the aqueous compartment by the solubilisates of short chain length. Acetic acid and the acetate, propionate, butanoate, and pentanoate ions spend an appreciable amount of time in the aqueous region. An estimate has been made of these distributions based on reasonable assumptions.


2019 ◽  
Vol 60 (4) ◽  
pp. 755-790 ◽  
Author(s):  
Christopher J Grose ◽  
Juan C Afonso

Abstract We examine REE (Rare-Earth Element) and isotopic (Sr–Hf–Nd–Pb) signatures in OIB (Ocean Island Basalts) as a function of lithospheric thickness and show that the data can be divided into thin- (&lt;12 Ma) and thick-plate (&gt;12 Ma) sub-sets. Comparison to geophysically constrained thermal plate models indicates that the demarcation age (∼12 Ma) corresponds to a lithospheric thickness of about 50 km. Thick-plate OIB show incompatible element and isotopic enrichments, whereas thin-plate lavas show MORB-like or slightly enriched values. We argue that enriched signatures in thick-plate OIB originate from low-degree melting at depths below the dry solidus, while depleted signatures in MORB and thin-plate OIB are indicative of higher-degree melting. We tested quantitative explanations of REE systematics using melting models for homogeneous fertile peridotite. Using experimental partition coefficients for major upper mantle minerals, our equilibrium melting models are not able to explain the data. However, using a new grain-scale disequilibrium melting model for the same homogeneous lithology the data can be explained. Disequilibrium models are able to explain the data by reducing the amount of incompatible element partitioning into low degree melts. To explore new levels of detail in disequilibrium phenomena, we employ the Monte-Carlo Potts model to characterize the textural evolution of a microstructure undergoing coarsening and phase transformation processes simultaneous with the diffusive partitioning of trace elements among solid phases and melt in decompressing mantle. We further employ inverse methods to study the thermochemical properties required for models to explain the OIB data. Both data and theory show that OIB erupted on spreading ridges contain signatures close to MORB values, although E-MORB provides the best fit. This indicates that MORB and OIB are produced by compositionally indistinguishable sources, although the isotopic data indicate that the source is heterogeneous. Also, a posteriori distributions are found for the temperature of the thermomechanical lithosphere-asthenosphere boundary (TLAB), the temperature in the source of OIB (Tp, oib) and the extent of equilibrium during melting (i.e. grain size). TLAB has been constrained to 1200–1300°C and Tp, oib is constrained to be &lt;1400°C. However, we consider the constraints on Tp, oib as a description of all OIB to be provisional, because it is a statistical inference from the global dataset. Exceptional islands or island groups may exist, such as the classical ‘hotspots’ (Hawaii, Reunion, etc) and these islands may originate from hot sources. On the other hand, by the same statistical arguments their origins may be anomalously hydrated or enriched instead. Mean grain size in the source of OIB is about 1–5 mm, although this is also provisional due to a strong dependence on knowledge of partition coefficients, ascent rate and the melting function. We also perform an inversion in which partition coefficients were allowed to vary from their experimental values. In these inversions TLAB and Tp, oib are unchanged, but realizations close to equilibrium can be found when partition coefficients differ substantially from their experimental values. We also investigated bulk compositions in the source of OIB constrained by our inverse models. Corrections for crystallization effects provided ambiguous confirmations of previously proposed mantle compositions, with depleted mantle providing the poorest fits. We did not include isotopes in our models, but we briefly evaluate the lithospheric thickness effect on isotopes. Although REE data do not require a lithologically heterogeneous source, isotopes indicate that a minor enriched component disproportionately contributes to thick-plate OIB, but is diluted by high-degree melting in the generation of thin-plate OIB and MORB.


Energies ◽  
2020 ◽  
Vol 13 (17) ◽  
pp. 4300
Author(s):  
Kosuke Sasakura ◽  
Takeshi Aoki ◽  
Masayoshi Komatsu ◽  
Takeshi Watanabe

Data centers (DCs) are becoming increasingly important in recent years, and highly efficient and reliable operation and management of DCs is now required. The generated heat density of the rack and information and communication technology (ICT) equipment is predicted to get higher in the future, so it is crucial to maintain the appropriate temperature environment in the server room where high heat is generated in order to ensure continuous service. It is especially important to predict changes of rack intake temperature in the server room when the computer room air conditioner (CRAC) is shut down, which can cause a rapid rise in temperature. However, it is quite difficult to predict the rack temperature accurately, which in turn makes it difficult to determine the impact on service in advance. In this research, we propose a model that predicts the rack intake temperature after the CRAC is shut down. Specifically, we use machine learning to construct a gradient boosting decision tree model with data from the CRAC, ICT equipment, and rack intake temperature. Experimental results demonstrate that the proposed method has a very high prediction accuracy: the coefficient of determination was 0.90 and the root mean square error (RMSE) was 0.54. Our model makes it possible to evaluate the impact on service and determine if action to maintain the temperature environment is required. We also clarify the effect of explanatory variables and training data of the machine learning on the model accuracy.


1976 ◽  
Vol 23 (2) ◽  
pp. 91-95
Author(s):  
SHIGERU MATSUKURA ◽  
HIDEAKI HIGASHINO ◽  
NOBORU SAKAMOTO ◽  
YUKIO HIRATA ◽  
HIROO IMURA

2016 ◽  
Vol 45 (47) ◽  
pp. 18954-18966 ◽  
Author(s):  
Zichao Ye ◽  
Lito P. de la Rama ◽  
Mikhail Y. Efremov ◽  
Jian-Min Zuo ◽  
Leslie H. Allen

Synthesis of single crystal silver alkanethiolate (any chain length) lamellae with highly ordered chain conformations, interlayer interfaces and intralayer lattices.


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