Amine Dynamics in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.

Variable-temperature 15N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an important family of CO2 capture materials. The results imply both bound and free amine nitrogen environments exist when diamines are coordinated to the framework open Mg2+ sites. There are rapid exchanges between two nitrogen environments for all three diamines, the rates and energetics of which are quantified by 15N solid-state NMR data and corroborated by density functional theory calculations and molecular dynamics simulations. The activation energy for the exchange provides a measure of the metal-amine bond strength. The unexpected negative correlation between the metal-amine bond strength and CO2 adsorption step pressure reveals that metal-amine bond strength is not the only important factor in determining the CO2 adsorption properties of diamine-appended Mg2(dobpdc) metal-organic frameworks

Efficient Numerical Full-Polarized Facet-Based Model for EM Scattering from Rough Sea Surface within a Wide Frequency Range

A full-polarized facet based scattering model (FPFSM) for investigating the electromagnetic (EM) scattering by two-dimensional electrically large sea surfaces with high efficiency at high microwave bands is proposed. For this method, the scattering field over a large sea facet in a diffuse scattering region is numerically deduced according to the Bragg scattering mechanism. In regard to near specular directions, a novel approach is proposed to calculate the scattered field from a sea surface based on the second order small slope approximation (SSA-II), which saves computer memory considerably and is able to analyze the EM scattering by electrically large sea surfaces. The feasibility of this method in evaluating the radar returns from the sea surface is proved by comparing the normalized radar cross sections (NRCS) and the Doppler spectrum with the SSA-II. Then NRCS results in monostatic and bistatic configurations under different polarization states, scattering angles and wind speeds are analyzed as well as the Doppler spectrum at Ka-band. Numerical results show that the FPFSM is a reliable and efficient method to analyze the full-polarized scattering characteristics from electrically large sea surface within a wide frequency range

Exergy Analysis of Alternative Configurations of Biomass-Based Light Olefin Production System with a Combined-Cycle Scheme via Methanol Intermediate

Thermodynamic performance of three conceptual systems for biomass-derived olefin production with electricity cogeneration was studied and compared via exergy analysis at the levels of system, subsystem and operation unit. The base case was composed of the subsystems of gasification, raw fuel gas adjustment, methanol/light olefin synthesis and steam & power generation, etc. The power case and fuel case were designed as the combustion of a fraction of gasification gas to increase power generation and the recycle of a fraction of synthesis tail gas to increase olefin production, respectively. It was found that the subsystems of gasification and steam & power generation contribute ca. 80% of overall exergy destruction for each case, of which gasifier and combustor are the main exergy destruction sources, due to the corresponding chemical exergy degrading of biomass and fuel gas. The low efficiency of 33.1% for the power case could be attributed to the significant irreversibility of the combustor, economizer, and condenser in the combined-cycle subsystem. The effect of the tail gas recycle ratio, moisture content of feedstock, and biomass type was also investigated to enhance system exergy performance, which could be achieved by high recycle ratio, using dry biomass and the feedstock with high carbon content. High system efficiency of 38.9% was obtained when oil palm shell was used, which was 31.7% for rice husk due to its low carbon content

In vivo cytological and chemical analysis of Casparian strips using stimulated Raman scattering microscopy

The Casparian strip, a barrier to the apoplastic movement of solutes from the cortex to the stele, is essential for the exclusion of salts, selective nutrient uptake, and many other processes. To date, extensive studies have focused on the physiological functions of endodermal Casparian strips. However, the chemical deposition nature of Casparian strips, as well as its relevance with respect to diffusion barrier functions, remains to be further elucidated. Here, we revealed three developmental stages of Casparian strips in maize primary roots using a traditional fluorescent staining method. Apoplastic permeability tests demonstrated that the barrier function of Casparian strips is largely related to their developmental stage and the pattern of lignin and suberin deposits. Fourier transform infrared (FTIR) analysis showed that the Casparian strips from the roots exhibited significant absorption bands characteristic of lignin and suberin, implying that the Casparian strips in maize primary roots consist largely of lignin and suberin. Furthermore, we developed a new method for label-free, in vivo structural, and biochemical analysis of Casparian strips based on stimulated Raman scattering (SRS) microscopy. Using SRS microscopy, we found that lignin and suberin accumulate simultaneously during the Casparian strip formation process. Based on these results, we propose a potential application of SRS for the chemical composition analysis of plant Casparian strips in situ

Elucidation of the corrosion rate enhancement mechanism in Mg–Er–Gd–Ni alloys with high volume fraction of LPSO phase and different Gd contents after extrusion

The microstructure evolution and corrosion mechanism of Mg–9Er–xGd–2Ni alloys, subjected to Gd addition and extrusion, were investigated in this study. Results shows that with the increase in Gd content from 1.0 wt.% to 5.0 wt.%, the second phase change from continuous network LPSO phase with intragranular γʹ phase to a monolithic continuous network LPSO phase, while the corresponding volume fraction of the second phase remains essentially unchanged. Moreover, it is noted that increasing Gd content contributed to a reduction in the corrosion rate of alloy by reducing galvanic corrosion couples and facilitating the formation of double Gd2O3 and Er2O3 corrosion-resistant films. Ultimately, what's most noteworthy is that compared with as-cast alloys, the corrosion rate of as-extruded alloys increased by 49.2%–125.3% with increasing Gd content, which is due to the streamlined LPSO phase distribution weakening the corrosion barrier effect of high-volume fraction network distribution LPSO phase alloy and grain refinement providing more corrosion interfaces that inhibited the formation of corrosion-resistant product films. This study provides new provides new insights for the development of highly degradable Mg–Er–Gd–Ni alloys that have high strength potential for applications in unconventional oil and gas extraction

Palladium-Catalyzed Asymmetric Addition of Diarylphosphines to α,β-Unsaturated Sulfonic Esters for the Synthesis of Chiral Phosphine Sulfonate Compounds

Highly stereoselective addition of diarylphosphines to α,β-unsaturated sulfonic esters catalyzed through a PCP pincer–Pd complex is developed to synthesize chiral phosphine sulfonic esters with excellent enantioselectivity (up to 99.5% ee). The transformation of the chiral adduct into a useful palladium phosphine sulfonate complex is also demonstrated

Asymmetric Michael Addition of Substituted Rhodanines to α,β-Unsaturated Ketones Catalyzed by Bulky Primary Amines

A bulky group was introduced by design into a diamine catalyst, and a series of robust and tunable bulky chiral primary amine catalysts were developed and successfully applied in the direct conjugate addition of substituted rhodanines to α,β-unsaturated ketones. High yields (up to 99%) and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 98% ee) were observed

Asymmetric Michael Addition of Substituted Rhodanines to α,β-Unsaturated Ketones Catalyzed by Bulky Primary Amines

A bulky group was introduced by design into a diamine catalyst, and a series of robust and tunable bulky chiral primary amine catalysts were developed and successfully applied in the direct conjugate addition of substituted rhodanines to α,β-unsaturated ketones. High yields (up to 99%) and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 98% ee) were observed

Asymmetric Michael Addition of Substituted Rhodanines to α,β-Unsaturated Ketones Catalyzed by Bulky Primary Amines

A bulky group was introduced by design into a diamine catalyst, and a series of robust and tunable bulky chiral primary amine catalysts were developed and successfully applied in the direct conjugate addition of substituted rhodanines to α,β-unsaturated ketones. High yields (up to 99%) and excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 98% ee) were observed