Mechanistic implications of the solvent kinetic isotope effect in the hydrolysis of NaBH4

The sodium borohydride, NaBH₄, hydrolysis mechanism is studied via the H₂O/D₂O kinetic isotope effect (KIE). This reaction is of importance as NaBH₄ is considered as a hydrogen storage material. Nowadays, hydrogen is thought to be one of the most promising and efficient clean energy carriers. In order to control the rate of the hydrogen evolution reaction (HER), one has to understand the mechanism of its production. The H₂O/D₂O KIE of the reactions of NaBH₄ and NaBD₄ with water was studied in solutions containing a ratio of H₂O/D₂O = 1.00. The separation factor, α, of both reactions is α = 5.0 ± 1.0. The rate of the hydrolysis of BD₄^? in H₂O is faster than that of BH₄^?. The results point out that the rate-determining step in all hydrolysis stages is the H–OH bond scission.     

Transgenerational Effects of Di(2-Ethylhexyl) Phthalate on Anogenital Distance,Sperm Functions and DNA Methylation in Rat Offspring

Di(2-ethylhexyl) phthalate (DEHP) is widely used as a plasticizer in the manufacture of polyvinylchloride plastics and has been associated with concerns regarding male reproductive toxicity. In this study, we hypothesized that maternal exposure to DEHP induces transgenerational inheritance of adult-onset adverse reproductive outcomes through the male germline in the F1, F2, and F3 generations of male offspring. Pregnant rats were treated with 5 or 500 mg of DEHP/kg/day through gavage from gestation day 0 to birth. The offspring body weight, anogenital distance (AGD), anogenital index (AGI), sperm count, motility, and DNA fragmentation index (DFI) were measured for all generations. Methyl-CpG binding domain sequencing was performed to analyze sperm DNA methylation status in the F3. DEHP exposure at 500 mg/kg affected AGD, AGI, sperm count, mean DFI, and %DFI in the F1; AGD, sperm count, and mean DFI in the F2; and AGD, AGI, mean DFI, and %DFI in the F3. DEHP exposure at 5 mg/kg affected AGD, AGI, sperm count, and %DFI in the F1; sperm count in the F2; and AGD and AGI in F3. Compared with the control group, 15 and 45 differentially hypermethylated genes were identified in the groups administered 5 mg/kg and 500 mg/kg DEHP, respectively. Moreover, 130 and 6 differentially hypomethylated genes were observed in the groups administered 5 mg/kg and 500 mg/kg DEHP. Overall, these results demonstrated that prenatal exposure to DEHP caused transgenerational epigenetic effects, which may explain the observed phenotypic changes in the male reproductive system.     

Revisit the Pitot static tubes in the standards

A Pitot tube is a popular device used for the measurements of flow fields. To control the accuracy of the Pitot tube coefficient, the international standard organization (ISO), the American Society for Testing and Materials (ASTM), and the Japanese Industrial Standards (JIS) issued guidelines that recommended the shape and working conditions of these devices. However, many Pitot tubes on the market do not follow these guidelines. In the present study, various types of Pitot tubes in the market were tested at the National Metrology Institute of Japan (NMIJ) to determine the effects of the geometry and flow characteristics. The results revealed certain limitations in the existing ISO and JIS standards, specifically with regard to the recommended design parameters of the AMCA Pitot tube, the reference coefficient value for the JIS Pitot tube, and the redefinition and limitation of Reynolds numbers pertaining to Pitot tube working conditions.     

Harvesting Air and Light Energy via “All-in-One” Polymer Cathodes for High-Capacity,Self-Chargeable,and Multimode-Switching Zinc Batteries

Aqueous rechargeable Zinc (Zn)–polymer batteries are promising alternatives to prevalent Li-ion cells in terms of cost, safety, and rate capability but they suffer from limited specific capacity in addition to poor environmental adaptability. Herein, air and light are successfully utilized from external environments in single near-neutral two-electrode Zn batteries to enable remarkably improved electrochemical performance, fast self-charging, and switchable multimode-operation from Zn–polymer to Zn–air cells. This system is enabled by a well-designed polyaniline-nanorod-array based “all-in-one” cathode combining reversible redox capability, oxygen reduction activity, and photothermal-responsiveness. The initiative design allows perfect integration of multiple energy harvesting from ambient “air” and light, energy conversion, and storage in one single cathode. Thus, it can act as an efficient light-assisted electrically-rechargeable Zn–polymer cell featuring the highest specific capacity of 430.0 mAh g⁻¹ among all existing polymer cathodes. Without external power sources, it can be self-charged to deliver a high discharging capacity of 363.1 mAh g⁻¹ by concurrently harvesting chemical energy from air and light energy for only 20 min. It can also switch to a light-responsive Zn–air battery mode to surmount the output capacity limit of Zn–polymer battery mode for continued electricity supply.     

A Terahertz Video Camera Patch Sheet with an Adjustable Design based on Self-Aligned, 2D,Suspended Sensor Array Patterning

Terahertz (THz) imaging is expected to become powerful tools for non-destructive inspections. To ensure the practical use of THz non-destructive monitoring, versatile THz imagers with adjustable designs that can eliminate the complexities and the bulkiness of the device are urgently required. Herein, a self-aligned filtration process for a 2D, free-standing carbon nanotube film array and its application to a THz video camera patch are reported. The presented techniques enable a) to freely design the camera size, sensor array pattern, and suspended shape according to its applications, b) to cut the camera patch into desired shapes, and c) to attach them to the objects that are intended to be measured. Real-time, non-destructive monitoring of various infrastructures is demonstrated. These results indicate that it can function regardless of restrictions, such as the shapes and locations of the measurement samples, thus providing a strong possibility for use in future non-destructive sensor networks.     

Analytical modeling of complex contact behavior between rock mass and lining structure

Based on the nondestructive test data of operating railway tunnels in China, this paper summarizes the basic characteristics of the complex contact behavior between the rock mass and lining structure. The contact modes are classified into dense contact, local non-contact, and loose contact. Subsequently, the corresponding mechanical model for each contact mode is developed according to its mechanical characteristics using the complex variable method. In the proposed mechanical model, a special algorithm is introduced to detect whether the local non-contact zone is re-contacted. Besides, a novel conformal mapping method is also proposed to accurately calculate the mechanical response of the concrete lining. Finally, the accuracy of the proposed method is verified by comparing it with the finite element method (FEM). Several parameter investigations are conducted to analyze the effects of different contact modes on the rock–lining interaction. The results show that: (i) the height of the local non-contact area does not have a significant effect on the contact stress distribution if no re-contact occurs; (ii) backfill grouting can reduce the local stress concentration caused by poor contact modes; and (iii) reducing the friction coefficient of the interface can lead to a more uniform distribution of internal forces in the concrete lining.     

Ferroelectric and electromechanical performance of diverse engineered states of Mn-doped 0.75Pb(Mg1/3Nb2/3)O3-0.25PbTiO3 ceramics

The materials processing history has a great influence on their properties and finally determines their application effect. In this paper, the ferroelectric, polarization-switching current, and strain properties of Mn-doped 0.75Pb(Mg_1/3Nb_2/3)O₃-0.25PbTiO₃ ceramics were studied in fresh state, aged state, and poled state, respectively. Compared with the symmetric polarization-electric-field (P-E) hysteresis loops, current-density-electric-field (J-E) curves, and bipolar electric-field-induced strain (S-E) curves in fresh state samples, asymmetric P-E loops, J-E curves, and bipolar S-E curves were obtained in poled state samples. Well-aged-state samples exhibit double hysteresis P-E loop, four peaks J-E curves, and symmetric S-E curves without negative strain. The symmetry-conforming short-range order (SC-SRO) principle of point defects and internal electric field E_i is employed to clarify the different phenomenon of three states. Results indicated that randomly oriented defect polarization P_D in aged samples can reverse the spontaneous polarization P_S back and result in the double hysteresis P-E loop and four peaks J-E curves. The oriented P_D and resulting E_i in poled-state samples will lead to the asymmetric loops and strain memory effect.     

Inorganic Nanoparticles Applied as Functional Therapeutics

Inorganic nanoparticles (NPs) offer significant advantages to the biomedical field owing to their large surface area, controllable structures, diverse surface chemistry, and unique optical and physical properties. Researchers worldwide have shown that inorganic NPs and the released metal ions can act as therapeutic agents in targeted tissues or to cure various diseases without acute toxicity. In this progress report, the recent developments in inorganic NPs with different compositions directly used as therapeutics are discussed. First, the recent convergence of nanotechnology and biotechnology in biomedical applications as well as the unique functions, features, and advantages of inorganic NPs in biomedical applications are summarized. Thereafter, the biological effects of inorganic compositions in NPs which include balancing the intracellular redox environment, regulating the specific cellular signaling and cellular behaviors, and apoptosis are explained. In addition, the emerging therapeutic applications of inorganic NPs in various diseases are exemplified. Finally, the perspectives and challenges for overcoming the weaknesses of inorganic NPs as therapeutics are discussed. By carefully considering and investigating the biological effects of inorganic NPs and metal ions released from NPs, more promising inorganic NPs based therapeutic agents can be developed.     

木质纤维与水泥共同改良软土的力学性能与微观机制分析

通过压实试验、无侧限抗压强度试验和劈裂试验,分析不同木质纤维含量、水泥含量和固化时间对软土力学性能的影响规律,探讨木质纤维、水泥改良软土的微观机制。结果表明,木质纤维的加入对水泥改良软土的击实特性有显著的影响;木质纤维与水泥可有效改善土体的抗压和劈裂抗拉强度,随着木质纤维含量的增加,改良土的抗压和劈裂抗拉强度呈现出明显的“驼峰”现象,并在木质纤维含量为0.25%时最大;木质纤维与水化产物、软土颗粒形成互锁效应,增大了改良土的摩擦力,同时木质纤维还承担一定的拉伸强度,使改良土的劈裂强度增加。