A new method was presented to estimate the strength distribution of hydrogen bonds in coal. The hydrogen bonds include the coal intramolecule hydrogen bonds and coal-water hydrogen bonds formed by hydroxyls in coal. The method analyzes the FTIR spectrum ranging from 2400 to 3700 cm -1 obtained using the in-situ diffuse reflectance IR Fourier transform (DRIFT) technique with neat, undiluted, coal samples. The FTIR spectra during the heat-up of eight coals (seven Argonne premium coals and an Australian brown coal), an ion-exchange resin, and a lignin were measured every 20 °C from room temperature to 300 °C. Each spectrum was divided into six hydrogen-bonded absorption bands by a curve-resolving method, then the amount of hydroxyls contributing to each hydrogen bond was estimated by Beer's law by using different absorptivity for each band. The strength of each hydrogen bond was estimated using a relation presented by Drago et al. that is known as one of the "linear enthalpy-spectroscopic shift relations". Using this analysis method, changes in hydrogen bond distributions (HBD) with increasing temperature were successfully estimated for all the samples examined. By utilizing the HBD the changes in enthalpies associated with the desorption of adsorbed water, the glass transition, and the decomposition of COOH groups were well estimated. Only FTIR spectra measurements were found to be enough to obtain such enthalpies. This greatly simplified the calculation procedure and increased the accuracy of the enthalpies. The validity of the proposed in situ FTIR measurement method and the analysis method for obtaining HBD was well clarified.
FeF3 is a promising cathode material for lithium batteries with a very high energy density due to its complete reduction to a mixture of LiF and Fe. The material is not yet practical due to a greater than 1 V hysteresis during charge and discharge. Previous work has suggested that this hysteresis might be intrinsic due to different reaction pathways. We employ galvanostatic intermittent titration (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) to study the reaction thermodynamics and kinetics. GITT experiments, when the electrode is allowed to rest for 72 h following a discharge or charge step, show that the hysteresis is 280 mV, in contrast to >1 V observed previously with slow rate charge and discharge experiments. CV results obtained in different potential ranges indicate that the apparent hysteresis is mostly due to the large overpotential needed to overcome the energy barrier for the nucleation of the LiF/Fe composite phases. EIS results are consistent with the formation of the nanocomposite. Further, EIS results indicate that extended rest of the electrode under open circuit appears to result in coalescence of the Fe nanoparticles, which reduces the Fe/LiF interfacial area. This hypothesis is also consistent with our observation that the charge–discharge overpotentials at high rates are smaller than what the Ohmic law would dictate. On the basis of these results, a reaction mechanism for the reaction is presented. The mechanism also points to potential approaches to mitigate the hysteresis through nanoengineering of the material.
BackgroundThree recent genome-wide association studies (GWASs) have reported that three SNPs (rs4072037, rs13361707 and rs2274223) located on genes related to host inflammatory response are significantly associated with susceptibility to gastric cancer (GC) in Chinese populations. Helicobacter pylori infection is also an important risk factor for GC through causing inflammatory response in the gastric mucosa. However, no study has established whether there are potential gene-environment interactions between these genetic variants and H. pylori infection to the risk of GC.MethodsWe genotyped three polymorphisms (rs4072037 at 1q22, rs13361707 at 5p13, and rs2274223 at 10q23) in 335 Chinese gastric adenocarcinoma patients and 334 controls. H. pylori serology was examined by enzyme-linked immunosorbent assay. Multivariable logistic regression models were used to evaluate the association between the variables and GC risk.ResultsWe confirmed that the three SNPs (rs4072037, rs13361707 and rs2274223) were significantly associated with GC susceptibility. H. pylori infection also significantly increased the risk of GC. Furthermore, there were joint effects between H. pylori infection and the three SNPs on the risk of GC. The most elevated risk of GC was found in subjects with H. pylori seropositivity and AA genotypes for rs4072037 [odds ratio (OR), 3.95; 95% confidence interval (CI), 2.29–6.79], H. pylori seropositivity and CT/CC genotypes for rs13361707 (OR, 2.68; 95% CI, 1.62–4.43), H. pylori seropositivity and AG/GG genotypes for rs2274223 (OR, 2.45; 95% CI, 1.55–3.88) compared with those with H. pylori seronegativity and other genotypes of each SNP. Significant interactions were observed between H. pylori seropositivity and the three SNPs (all P G× E <0.05) to the risk of GC.ConclusionThese findings indicate that the three SNPs (rs4072037, rs13361707 and rs2274223) identified in the GWASs may interact with H. pylori infection to increase the risk of GC.
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