Evaluation of the degree of rate control via automatic differentiation

The degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate-limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady-state and transient kinetics. Furthermore, we illustrate a hybrid local-global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high-quality results efficiently.     

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF₃ and MgF₂ were used as sintering aids in the fabrication of Si₃N₄ ceramics via gas pressure sintering (GPS). The synergistic effects of YF₃ and MgF₂ on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si₃N₄ ceramics were investigated. The results showed that appropriately adjusting the YF₃/MgF₂ ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF₃ and 2 mol% MgF₂ achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol^?1) as well as the highest thermal conductivity (83 W m^?1 K^?1) and fracture toughness (8.82 ± 0.13 MPa m^1/2).     

The overall crystallization behavior of polyethylene/wax blends as phase change materials for thermal energy storage: A mini review

This review paper deals with the overall crystallization behavior of polyethylene/wax blends as phase change materials (PCMs) for thermal energy storage with the determination of their thermal properties. The addition of molten wax to the polyethylenes decreases the crystallization and melting temperatures of the blends. However, incorporating fillers to the polyethylene/wax blends can either decrease or increase the crystallization and melting temperatures of the composites depending on the filler type. The normalized enthalpy values of linear low-density polyethylene showed no significant change when increasing the wax content. On the contrary, the normalized enthalpy values of the wax in the blends were lesser than that of pure wax and increased with increasing wax content. Since the wax in the blend had a lower crystallinity compared to pure wax, this influences its effectiveness as a PCM for thermal energy storage. The effect of different polyethylenes on the wax morphology gave rise to enhance phase separation when wax was blended to high-density polyethylene as compared to the other polyethylenes. On the contrary, the effect of various waxes on the morphology of polyethylene resulted in different morphologies due to the molecular weight of the wax used and the structure of the polyethylene chain. The addition of fillers to the polyethylene (PE)/wax samples resulted in enhanced phase separation. The overall isothermal crystallization rate and the equilibrium melting temperature of PEs in the PEs/wax blends were depressed by wax addition due to the wax dilution effect.     

Synthesis and Initial Characterization of a Selective,Pseudo-irreversible Inhibitor of Human Butyrylcholinesterase as PET Tracer

The enzyme butyrylcholinesterase (BChE) represents a promising target for imaging probes to potentially enable early diagnosis of neurodegenerative diseases like Alzheimer's disease (AD) and to monitor disease progression in some forms of cancer. In this study, we present the design, facile synthesis, in vitro and preliminary ex vivo and in vivo evaluation of a morpholine-based, selective inhibitor of human BChE as a positron emission tomography (PET) tracer with a pseudo-irreversible binding mode. We demonstrate a novel protecting group strategy for ¹⁸F radiolabeling of carbamate precursors and show that the inhibitory potency as well as kinetic properties of our unlabeled reference compound were retained in comparison to the parent compound. In particular, the prolonged duration of enzyme inhibition of such a morpholinocarbamate motivated us to design a PET tracer, possibly enabling a precise mapping of BChE distribution.     

羧基含氟聚合物纳米纤维膜的制备及对铜(II)的吸附性能

以甲基丙烯酸十二氟庚酯(DFHMA)和甲基丙烯酸(MAA)为单体,通过溶液聚合法制备出共聚物DFHMA-co-MAA,将DFHMA-co-MAA与聚偏氟乙烯(PVDF)按一定质量共混,采用静电纺丝方法,制备出羧基含氟聚合物(PVDF-DM)纳米纤维膜,用以吸附溶液中Cu(II)。讨论了PVDF和DFHMA-co-MAA的质量配比对纤维微观形貌和对Cu(II)吸附性能的影响,得出当PVDF与DFHMA-co-MAA的质量比为1∶2时,纤维的微观直径较均一且吸附性能最佳,故实验采用该质量配比制备PVDF-DM。使用红外光谱对PVDF-DM进行表征,显示出PVDF-DM纤维膜中含有—OH和C＝O等活性吸附基团。以PVDF-DM纳米纤维膜为吸附剂,探讨了吸附剂用量、吸附pH值和吸附时间对Cu(II)吸附性能的影响,并研究了吸附过程的动力学模型。结果表明,室温下,当吸附剂用量为0.03g,pH=5时,吸附60min达到吸附平衡,吸附率和吸附量分别为94.37%和62.91mg/g,PVDF-DM纳米纤维膜对Cu(II)的吸附过程同时满足拟一级动力学和拟二级动力学模型,说明该吸附过程包含了化学吸附和物理吸附。PVDF-DM纳米纤维膜循环使用5次后,吸附能力仅降低16.23%,说明PVDF-DM纳米纤维膜具有很好的再生使用能力。     

聚乙烯亚胺氨基化磁性氧化石墨烯的制备及其对活性艳红X-3B的吸附

使用改性hummers法制备出氧化石墨烯(GO),通过水热法在GO上生长磁性CoFe₂O₄,再使用聚乙烯亚胺(PEI)进行氨基改性,制备出聚乙烯亚胺氨基化磁性氧化石墨烯(PEI-MGO)。使用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对PEI-MGO的结构和微观形貌进行表征。结果表明:纳米级尖晶石相CoFe₂O₄均匀分散于GO上,且氨基改性成功。探讨了PEI-MGO对水体中活性艳红X-3B的吸附性能。结果表明:在活性艳红X-3B初始质量浓度为150mg/L、体积为100mL、吸附剂质量为0.04g、pH值为1、吸附时间为60min时达到平衡,平衡吸附量为361.15mg/g。PEI-MGO对活性艳红X-3B的饱和吸附量为470.58mg/g。磁分离和磁回收研究表明,PEI-MGO能快速从水体中分离,回收率为98.6%。     

Prediction of methane adsorption content in continental coal-bearing shale reservoir using SLD model

Shale gas, as an important unconventional resource, has drawn global attention. It is mainly composed of adsorption gas and free gas. Adsorption gas content could play an important guiding role on both the selection of favorable perspective area and the exploration and exploitation of shale gas resources. In order to accurately measure adsorption gas content, a new approach was established to predict the adsorption isotherm of methane on shale. Based on the simplified local-density (SLD) method, both the adsorption isotherms of illite, illite/smectite mixed-layer, cholorite and type III kerogen and the total shale rock could be well fitted. The fitting results show good coincidences with the true experimental test data, which proves the method is reasonable and dependable and the prediction results are effective and credible. In addition, the good simulation results show that the SLD parameters can reflect the pore structure characteristics and corresponding adsorption characteristics of the shale samples, which can be used for the quantitative characterization of shale pore system.     

伊利石和高岭石对U(Ⅵ)的吸附

以伊利石和高岭石为吸附剂，通过静态吸附法研究了其对U(Ⅵ)的吸附特性。考察了接触时间、初始浓度、吸附剂质量、pH、温度、离子种类、腐殖酸等对其吸附效果的影响；采用红外光谱(FTIR) 对伊利石和高岭石的结构进行了表征。研究结果表明：伊利石和高岭石对U(Ⅵ)具有很强的吸附能力，在10 h、铀初始质量浓度为30 mg/L、吸附剂质量为0.04 g、pH=5的条件下，伊利石对U(Ⅵ)的吸附效果最好；在12 h、铀初始质量浓度为30 mg/L、吸附剂质量为0.01 g、pH=5的条件下，高岭石对U(Ⅵ)的吸附效果最好；随着温度的升高，伊利石和高岭石对U(Ⅵ)的吸附能力不断增强，尤其是伊利石；溶液中Mg²⁺、CO^2-₃、HCO^-₃显著降低了伊利石和高岭石对U(Ⅵ)的吸附效果；随着腐殖酸浓度的增加，伊利石对U(Ⅵ)的吸附能力提高，高岭石对U(Ⅵ)的吸附能力降低。     

微生物质水热碳锰复合材料对铀的吸附行为研究

以工业啤酒酵母为碳源，采用一步法合成了微生物质水热碳锰复合材料（MHTC），并利用XRD、FT-IR和SEM等对材料进行了表征。在此基础上，系统研究了不同C/Mn原子比、初始pH值、接触时间、初始铀浓度对MHTC吸附铀性能的影响。结果表明：C/Mn原子比为1∶10的碳锰复合材料（MHTC-10）对铀的吸附性能最优。在铀初始浓度为50 mg/L、初始pH=4.5条件下，12 h可达吸附平衡，最大吸附量为371 mg/g。吸附过程符合准二级动力学模型以及Freundlich等温模型。热力学数据表明，铀在MHTC-10上的吸附是一自发、放热的过程。该研究结果可为含铀环境中铀的分离富集提供新的思路。