Dramatic variation of magnetic exchange through double end-on azide bridges in a series of ladder-like copper(II) coordination polymers

Three ladder-like coordination polymers, [Cu2(phprpy)2-mu-(N3)2(N3)2], 1; [Cu2(terpy)2-mu-(N3)4Cu2-mu-(N3)2(N3)2], 2; and[Cu2(terpy)2-mu-(N3)2(N3)2Cu3-mu-(N3)4(N3)2], 3, consisting of Cu2+ ions with double end-on azide bridges were synthesized, their crystal structures and magnetic properties were determined, and spin dimer analysis was performed to explain the signs and strengths of their strong spin exchange interactions [phprpy is 4-(3-phenylpropyl)pyridine and terpy is 2,2':6,2'-terpyridine]. Although these compounds have ladder-like arrangements of Cu2+ ions, their magnetic structures are described as isolated dimers for 1 and 2 and as isolated trimers for 3. The predominant spin exchange paths in 1-3 have double end-on azide bridges linking adjacent Cu2+ ions, and the geometrical parameters of these bridging structures are similar. However, the spin dimer of 1 exhibits a strong ferromagnetic coupling; that of 2, a strong antiferromagnetic coupling; and that of 3, a weak ferromagnetic coupling. These findings are well explained by the present spin dimer analysis and show that the nature and geometry of the nonbridging ligands can have a strong influence on the sign and strength of the spin exchange interaction between Cu2+ ions connected by double end-on azide bridges.     

Electrochemical methods for the preparation of gold-coated TiO2 nanoparticles with variable coverages

We report here the first electrochemical methods to prepare elemental Au0-coated TiO2 nanoparticles with controllable coverages. First, Au substrates were cycled in a deoxygenated aqueous solution containing 0.1 N HCl and 1 mM TiO2 nanoparticles from -0.28 to +1.22 V versus Ag/AgCl at 500 mV/s with different numbers of scans. The durations at the cathodic and anodic vertexes were 10 and 5 s, respectively. After this process, positively charged Au-coated TiO2 nanoparticles were formed in the solutions. Then a cathodic overpotential of 0.6 V from the open circuit potential of ca. 0.82 V versus Ag/AgCl was applied under sonication to synthesize elemental Au0-coated TiO2 nanoparticles. The coverage of Au shells in the elemental Au-coated TiO2 nanoparticles is varied from 10% to 95% by increasing the number of scans from 10 to 50 in preparing the positively charged Au-coated TiO2 nanoparticles. The extremely high coverage of 95% in this study is notable, as compared with other methods to prepare Au-coated TiO2 nanoparticles.     

Sorption of cesium on rocks using heterogeneity-based isotherm models

Summary Sorption of radionuclides onto surrounding rocks play an important role in retarding the migration of radionuclides from a radioactive waste repository. The sorption isotherm model is usually used to describe the sorption behaviors and assess the sorption potential of radionuclides on rock. However, most of the studies to investigate the feasibility of isotherm models for the sorption of radionuclides are based on the assumption that the sorption energy is uniform and homogeneously distributed on the sorbent surfaces. In this study, two heterogeneity-based isotherms, Langmuir-Freundlich isotherm model (LF) and generalized-Freundlich isotherm model (GF), were used for the evaluation of the sorption characteristics of cesium on the selected Taiwan tuff and basalt. The sorption experiments in this study were carried out by batch method, and the experimental data were modeled by LF and GF heterogeneity-based isotherm models. The results showed that both of the LF and GF models could fit the data more perfectly than the Langmuir model. The heterogeneity of sorption onto tuff and basalt could be well characterized by the LF and GF models by means of the calculation and plotting of the affinity spectrum. The results showed that the sorption surface of tuff is more heterogeneous and complex than that of basalts.     

Investigation of the scanning tunneling microscopy image, the stacking pattern, and the bias-voltage-dependent structural instability of 1,10'-phenanthroline molecules adsorbed on Au(111) in terms of electronic structure calculations

A self-assembled monolayer of 1,10'-phenanthroline (phen) molecules on Au(111) was found to undergo a structural phase transition when the bias voltage is switched in scanning tunneling microscopy (STM) experiments (Phys. Rev. Lett. 1995, 75, 2376; Surf. Sci. 1997, 389, 19). The nature of two bright spots representing each phen molecule in the high-resolution STM images of phen molecules on Au(111) was identified by calculating the partial density plots for a monolayer of phen molecules adsorbed on Au(111) with tight-binding electronic structure calculations. The stacking pattern of chains of phen molecules on Au(111) was explained by studying the intermolecular interactions between phen molecules on the basis of first-principles electronic structure calculations for a phen dimer, (phen)(2). The structural instability of phen molecule arrangement caused by the bias-voltage switch was probed by estimating the adsorbate-surface interaction energy with the point-charge approximation for Au(111).     

A low-current Al-gate C-MOS crystal oscillator

The subthreshold properties of MOS transistors have been used advantageously to implement a crystal oscillator that operates at the sub-microampere current levels, using low-voltage metal-gate C-MOS technology. Composed of a reference current generator, a voltage-amplitude regulator, a Pierce oscillator, and an a.c. amplifier, the circuit can be put into a shutdown mode for power conservation.     

声速测量实验装置扩展应用

通过对声速测量装置进行适当的改进,使其既能测量空气中的声速,也能测量水、甘油等液体中的声速,减少重复购置仪器的投资,提高了仪器的利用率.     

Viromimetic STING Agonist‐Loaded Hollow Polymeric Nanoparticles for Safe and Effective Vaccination against Middle East Respiratory Syndrome Coronavirus

The continued threat of emerging, highly lethal infectious pathogens such as Middle East respiratory syndrome coronavirus (MERS‐CoV) calls for the development of novel vaccine technology that offers safe and effective prophylactic measures. Here, a novel nanoparticle vaccine is developed to deliver subunit viral antigens and STING agonists in a virus‐like fashion. STING agonists are first encapsulated into capsid‐like hollow polymeric nanoparticles, which show multiple favorable attributes, including a pH‐responsive release profile, prominent local immune activation, and reduced systemic reactogenicity. Upon subsequent antigen conjugation, the nanoparticles carry morphological semblance to native virions and facilitate codelivery of antigens and STING agonists to draining lymph nodes and immune cells for immune potentiation. Nanoparticle vaccine effectiveness is supported by the elicitation of potent neutralization antibody and antigen‐specific T cell responses in mice immunized with a MERS‐CoV nanoparticle vaccine candidate. Using a MERS‐CoV‐permissive transgenic mouse model, it is shown that mice immunized with this nanoparticle‐based MERS‐CoV vaccine are protected against a lethal challenge of MERS‐CoV without triggering undesirable eosinophilic immunopathology. Together, the biocompatible hollow nanoparticle described herein provides an excellent strategy for delivering both subunit vaccine candidates and novel adjuvants, enabling accelerated development of effective and safe vaccines against emerging viral pathogens.     

Comparison of Linear and Nonlinear Forms of Isotherm Models for Strontium Sorption on a Sodium Bentonite

Sorption on bentonite will play an important role in retarding the migration of radionuclides from a waste repository. Bentonite is characterized by low permeability, water swelling capability and excellent sorption potential for cationic radionuclides. To correctly assess the sorption potential of radionuclides on bentonite is essential for the development of predictive migration models. The sorption isotherm model is usually used to describe the sorption behavior and assess the sorption potential of radionuclides on bentonite. However, there are few studies to investigate the feasibility of isotherm models for the sorption of radionuclides on bentonite. Thus, in this study, we compared the goodness-of-fit of linear and nonlinear forms of two common isotherm models, Langmuir and Freundlich equations. The experimental sorption isotherms of strontium (Sr) on Wyoming bentonite, MX-80, were used for illustration. The results showed that the nonlinear forms of Langmuir and Freundlich isotherm models are more suitable for fitting the experimental sorption isotherms of Sr on MX-80 than are the linear forms. Thus, the nonlinear forms of isotherm models should be primarily adopted to fit experimental isotherms. On the other hand, we also found that the goodness-of-fit of Langmuir model is better than that of Freundlich model. Moreover, based on the theoretical assumptions of Langmuir isotherm model, the parameters M and K _L represent the sorption capacity and affinity, respectively. One can use the values of M and K _L , obtained from fitting the experimental isotherms, to assess the sorption potential of radionuclides in bentonite. Thus, we suggested that the Langmuir isotherm model is more useful for investigating the sorption behavior of radionuclides on bentonite.