Spectroscopic Studies of 1-Aryl-2,2-Dichlorocyclopropanes

Seventeen 1-aryl-2,2-dichlorocyclopropanes were examined by using IR, ¹³C NMR, and mass spectrometry. The data obtained from IR and ¹³C NMR spectra indicate that the bond strength of carbon-chlorine on the cyclopropane ring and the electron density of that carbon depend on the substituent. The mass fragmentation patterns of compounds in this series resemble those of the dibromo analogues. The fragmentation mechanism is proposed to involve the formation of indenium ion through an electrocyclization.     

AC calorimetric study of phase transitions in phosphatidylcholine-cholesterol systems

Using an ac calorimetric method, detailed behaviour of the heat capacity in dipalmitoyl-phosphatidylcholine-cholesterol system was studied in the cholesterol concentration less than 5 mol%. It was revealed that the heat capacity near the main transition was composed of at least four anomalies, i.e., multipeak took place in the heat capacity. This fact indicates that a simple theory explaining coexistence of two phases in two component systems does not work in the multipeak region. Then, relation between the multipeak heat capacity and the change of the ripple structure with the cholesterol concentration should be taken into account, when we consider thermodynamical behaviour of the systems.

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Zusammenfassung Mittels AC-Kalorimetrie wurde bei Cholesterol-Konzentrationen von weniger als 5 mol% das Verhalten der Wärmekapazität im System Dipalmitoylphosphatidylcholin-Cholesterol untersucht. Es wurde gezeigt, daß sich die Wärmekapazität in der Nähe der Hauptumwandlung aus mindestens vier Anomalien zusammensetzt, d.h. bei der Wärmekapazität kann ein Multipeak beobachtet werden. Diese Tatsache zeigt, daß eine einfache Theorie, welche die Koexistenz zweier Phasen in einem Zweikomponenten-System erklärt, für die Multipeakregion nicht geeignet ist. Weiterhin sollte bei Überlegungen zum thermodynamischen Verhalten von Systemen eine Beziehung zwischen der Multipeak-Wärmekapazität bzw. der Welligkeitsstruktur und der Cholesterol-Konzentration berücksichtigt werden.

     

含1,3-亚丙基冠醚的合成

为了进一步研究亚丙基冠醚的络合行为,合成了三种含1,3-亚丙基冠醚,即2,3-苯并-1,4,7,11-四氧-环十三-2-烯(苯并-13-冠-4)(1)、2,3-苯并-1,4,8,11,14-五氧-环十七-2-烯(苯并-17-冠-5)(2)、2,3-苯并-1,4,7,10,14,17-六氧-环十九-2-烯(苯并-19-冠-6)(3)。通过元素分析、红外光谱、质谱、核磁共振谱和 X-衍射晶体结构分析,确证了它们的结构。     

Synthesis of aminomethyl and amino analogs of 5-benzylacyclouridine and 5-benzyloxybenzylacyclouridine

Amino analogs of BAU (5-benzylacyclouridine) and BBAU (5-benzyloxybenzylacyclouridine) and their 2′-hydroxymethyl derivatives were synthesized for evaluation as inhibitors of uridine phosphorylase and hence potential cancer chemotherapeutic agents. Both aminomethyl analogs were found to be potent inhibitors of this enzyme and good potentiators of the anti-tumor action of FUdR.     

新型手性硫醚-亚磷酰胺配体的设计与应用

根据模块组合法原理,设计并合成了一种具有亚磷酰胺结构的硫醚配体,该配体具有原料便宜易得、合成步骤简单、易于修饰和结构稳定等特点。以配体/钯络合物催化的丙二酸二甲酯与1,3-二苯基烯丙基醋酸酯的烯丙基化反应作为模板反应,探究了溶剂、碱对其立体控制的影响。随后探究了中心手性与轴手性的匹配/错配现象以及硫醚片段的空间位阻、电性对反应立体控制的作用。在最佳条件下,产物的对映选择性能够达到-76% ee。     

Fine Pore-Structure Engineering by Ligand Conformational Control of Naphthalene Diimide-Based Semiconducting Porous Coordination Polymers for Efficient Chemiresistive Gas Sensing

Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore structure engineering by ligand conformation control of naphthalene diimide (NDI)-based semiconducting PCPs with π stacking-dependent conductivity tunability is achieved. The π stacking distances and ligand conformation in these isoreticular PCPs were modulated by employing metal centers with different coordination geometries. As a result, three conjugated PCPs (Co−pyNDI, Ni−pyNDI, and Zn−pyNDI) with varying pore structure and conductivity were obtained. Their crystal structures were determined by three-dimensional electron diffraction. The through-space charge transfer and tunable pore structure in these PCPs result in modulated selectivity and sensitivity in gas sensing. Zn−pyNDI can serve as a room-temperature operable chemiresistive sensor selective to acetone.     

High Power- and Energy-Density Supercapacitors through the Chlorine Respiration Mechanism

Supercapacitor represents an important electrical energy storage technology with high-power performance and superior cyclability. However, currently commercialized supercapacitors still suffer limited energy densities. Here we report an unprecedentedly respiring supercapacitor with chlorine gas iteratively re-inspires in porous carbon materials, that improves the energy density by orders of magnitude. Both electrochemical results and theoretical calculations show that porous carbon with pore size around 3 nm delivers the best chlorine evolution and adsorption performance. The respiring supercapacitor with multi-wall carbon nanotube as the cathode and NaTi₂(PO₄)₃ as the anode can store specific energy of 33 Wh kg⁻¹ with negligible capacity loss over 30 000 cycles. The energy density can be further improved to 53 Wh kg⁻¹ by replacing NaTi₂(PO₄)₃ with zinc anode. Furthermore, thanks to the extraordinary reaction kinetics of chlorine gas, this respiring supercapacitor performs an extremely high-power density of 50 000 W kg⁻¹.     

Synthesis and Application of Low Molecular Weight PEI-Based Copolymers for siRNA Delivery with Smart Polymer Blends

Polyethylenimine (PEI) is a commonly used cationic polymer for small-interfering RNA (siRNA) delivery due to its high transfection efficiency at low commercial cost. However, high molecular weight PEI is cytotoxic and thus, its practical application is limited. In this study, different formulations of low molecular weight PEI (LMW-PEI) based copolymers polyethylenimine-g-polycaprolactone (PEI–PCL) (800 Da–40 kDa) and PEI–PCL–PEI (5–5–5 kDa) blended with or without polyethylene glycol-b-polycaprolactone (PEG–PCL) (5 kDa-4 kDa) are investigated to prepare nanoparticles via nanoprecipitation using a solvent displacement method with sizes ≈100 nm. PEG–PCL can stabilize the nanoparticles, improve their biocompatibility, and extend their circulation time in vivo. The nanoparticles composed of PEI–PCL–PEI and PEG–PCL show higher siRNA encapsulation efficiency than PEI–PCL/PEG–PCL based nanoparticles at low N/P ratios, higher cellular uptake, and a gene silencing efficiency of ≈40% as a result of the higher molecular weight PEI blocks. These results suggest that the PEI–PCL–PEI/PEG–PCL nanoparticle system could be a promising vehicle for siRNA delivery at minimal synthetic effort.     

Designing Solid Electrolyte Interfaces towards Homogeneous Na Deposition: Theoretical Guidelines for Electrolyte Additives and Superior High-Rate Cycling Stability

Metallic Na is a promising metal anode for large-scale energy storage. Nevertheless, unstable solid electrolyte interphase (SEI) and uncontrollable Na dendrite growth lead to disastrous short circuit and poor cycle life. Through phase field and ab initio molecular dynamics simulation, we first predict that the sodium bromide (NaBr) with the lowest Na ion diffusion energy barrier among sodium halogen compounds (NaX, X=F, Cl, Br, I) is the ideal SEI composition to induce the spherical Na deposition for suppressing dendrite growth. Then, 1,2-dibromobenzene (1,2-DBB) additive is introduced into the common fluoroethylene carbonate-based carbonate electrolyte (the corresponding SEI has high mechanical stability) to construct a desirable NaBr-rich stable SEI layer. When the Na||Na₃V₂(PO₄)₃ cell utilizes the electrolyte with 1,2-DBB additive, an extraordinary capacity retention of 94 % is achieved after 2000 cycles at a high rate of 10 C. This study provides a design philosophy for dendrite-free Na metal anode and can be expanded to other metal anodes.     

In Situ Polymerized 1,3-Dioxolane Electrolyte for Integrated Solid-State Lithium Batteries

Solid-state lithium batteries are promising and safe energy storage devices for mobile electronics and electric vehicles. In this work, we report a facile in situ polymerization of 1,3-dioxolane electrolytes to fabricate integrated solid-state lithium batteries. The in situ polymerization and formation of solid-state dioxolane electrolytes on interconnected carbon nanotubes (CNTs) and active materials is the key to realizing a high-performance battery with excellent interfacial contact among CNTs, active materials and electrolytes. Therefore, the electrodes could be tightly integrated into batteries through the CNTs and electrolyte. Electrons/ions enable full access to active materials in the whole electrode. Electrodes with a low resistance of 4.5 Ω □⁻¹ and high lithium-ion diffusion efficiency of 2.5×10⁻¹¹ cm² s⁻¹ can significantly improve the electrochemical kinetics. Subsequently, the batteries demonstrated high energy density, amazing charge/discharge rate and long cycle life.