Efficient Capture and Low Energy Release of NH3 by Azophenol Decorated Photoresponsive Covalent Organic Frameworks.

In NH3 capture technologies, the desorption process is usually driven by high temperature and low pressure (such as 150-200°C under vacuum), which accounts for intensive energy consumption and CO2 emission. Developing light responsive adsorbent is promising in this regard but remains a great challenge. Here, we for the first time designed and synthesized a light responsive azophenol-containing covalent organic framework (COF), COF-HNU38, to address this challenge. We found that at 25 °C and 1.0 bar the cis -COF exhibited a NH3 uptake capacity of 7.7 mmol g-1 and a NH3/N2 selectivity of 158. In the adsorbed NH3, about 29.0% could be removed by vis-light irradiated cis-trans isomerization at 25 °C, and the remaining NH3 might be released at 25 °C under vacuum. Almost no decrease in adsorption capacity was observed after eight adsorption-desorption cycles. As such, an efficient NH3 capture and low energy release strategy was established thanks to the multiple hydrogen bond interactions (which are strong in total but weak in individuals) between NH3 and the smart COF, and the increase in polarity and in number of hydrogen bond sites after the trans-cis isomerization process.

Isomerization of DASA Molecules in the Nanopores of Metal-Organic Frameworks: What Determines Its Reversibility?

In recent years, light-responsive molecules have been incorporated in metal-organic frameworks (MOFs) to fabricate light-responsive intelligent devices, where reversible isomerization of the guest molecules in the nanopores is crucial. However, how to design a porous environment of MOFs to achieve a reversible isomerization remains unknown until now. In this work, donor-acceptor Stenhouse adducts (DASAs), a new kind of visible light responsive compound, were confined in the nanopores of different MOFs to study their isomerization upon visible-light irradiation/mild heating. We found that the polarity of the pore environment is the key to control the reversibility of isomerization of such guest molecules. Under the guidance of this principle, MIL-53(Al) was screened to investigate the proton conductivity and switching performance of the DASA-confined MOF. The proton conductance was up to 0.013 S cm-1 at 80 °C and 98 % RH, and at least 30 switching cycles were achieved thanks to the Grotthuss-type mechanism and the low polarity of MIL-53(Al) pore environment.

Anchoring LiCl in the Nanopores of Metal-Organic Frameworks for Ultra-High Uptake and Selective Separation of Ammonia.

Ammonia (NH3 ) is an important chemical raw material and a unique carbon-free fuel with high hydrogen energy density. Thus, NH3 capture, storage, and desorption are of significant importance. However, high capacity capture, low energy desorption, and selective separation of NH3 are still challengs so far. Here, we report high-performance hybrid sorbents by anchoring LiCl in the nanopores of MIL-53-(OH)2 metal-organic frameworks (MOFs). It is found that the optimal composite shows a capture capacity of 33.9 mmol g-1 NH3 at 1.0 bar and 25 °C, which far exceeds the current record among the reported porous materials. Notably, the excellent capture capacity at low pressure and high temperature makes it possible to selectively capture NH3 from NH3 /N2 , NH3 /CO2 , and NH3 /H2 O. It is revealed that synergistic action of NH3 coordination to the highly dispersed Li+ in the MOF nanopores and hydrogen bonding of NH3 with Cl- account for such an excellent capture and selectivity performance.

Population PK/PD model of tacrolimus for exploring the relationship between accumulated exposure and quantitative scores in myasthenia gravis patients.

Tacrolimus is an important immunosuppressant used in the treatment of myasthenia gravis (MG). However, the population pharmacokinetic (PK) characteristics together with the exposure-response of tacrolimus in the treatment of MG remain largely unknown. In this study, we aimed to develop a population PK/pharmacodynamic (PK/PD) model of tacrolimus in patients with MG, in order to explore the relationships among tacrolimus dose, exposure, and its therapeutic efficacy. The genotype of CYP3A5, Osserman's classification, and status of thymus, as well as demographic characteristics and other biomarkers from laboratory testing were tested as covariate, and simulations were performed based on the final model. The population PK model was described using a one-compartment model with first-order elimination and fixed absorption parameters. CYP3A5 genotype significantly influenced the apparent clearance, and total protein (TP) influenced the apparent volume of distribution as covariates. The quantitative MG scores were characterized by the cumulated area under curve of tacrolimus in a maximum effect function. Osserman's classification was a significant covariate on the initial score of patients with MG. The simulations demonstrated that tacrolimus showed an unsatisfying effect possibly due to insufficient exposure in some patients with MG. A starting dose of 2 mg/d and even higher dose for patients with CYP3A5 *1/*1 and *1/*3 and lower TP level were required for the rapid action of tacrolimus. The population PK/PD model quantitatively described the relationships among tacrolimus dose, exposure, and therapeutic efficacy in patients with MG, which could provide reference for the optimization of tacrolimus dosing regimen at the individual patient level.

[Advances in identification of Chinese medicines by NIRS].

This review addresses the latest situations and advances of near infrared spectroscopy (NIRS) in which detection of counterfeits and imitations, as well as monitoring origin and quality of Chinese crude drugs and Chinese patent medicines (CCDM) through consultation and summarization of relative literatures. On the one hand, NIRS gradually reveals its advantages and discriminating ability in the ways of nondestructive, rapid, simple, easy, and handy assessment. However NIRS still has some problems in representative samples and models stability for practice of CCDM. In order to keep up with popularization of NIRS in other areas, applications in detection of precious and/or priceless herbals, on-line quality control of valuable herbs, and screening of some chemicals illegally mixed into herbal preparations may be focused preferentially.

A record ammonia adsorption by calcium chloride confined in covalent organic frameworks.

Ammonia is a vital chemical raw material, but it is also a highly toxic environmenal pollutant. However, its highly efficient uptake and reversible release is a challenge. Herein, we have designed and synthesized a series of hybrid materials for efficient NH3 capture by confining calcium chloride (CaCl2) in a porous covalent organic framework (COF). A high capture capacity of 26.5 mmol g-1 is obtained at 25 °C and 1 bar, which is the highest value among existing porous materials, and NH3 can be easily desorbed at 80 °C under vacuum for 2 h. Particularly, the hybrid COF is highly efficient for the absorption of low NH3 content. Such excellent performance is ascribed to the highly dispersion of CaCl2 in the pores of the COF, and coordinating interaction of NH3 to Ca2+ together with hydrogen bond interaction between NH3 and Cl-.

Simultaneous determination of cyclosporine and tacrolimus in human whole blood by ultra-high performance liquid chromatography tandem mass spectrometry and comparison with a chemiluminescence microparticle immunoassay.

Overestimation of immunoassays for cyclosporine (CsA) and tacrolimus (TAC) analysis in human whole blood is a problem. The liquid chromatography tandem mass spectrometry is recommended as a golden method for CsA and TAC analysis. The aim of the study is to develop and validate an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of CsA and TAC in human whole blood and evaluate its agreement with a chemiluminescence microparticle immunoassay (CMIA). The UHPLC-MS/MS method for simultaneous determination of CsA and TAC in human whole blood was developed and validated according to the guidelines. A total of 177 CsA and 220 TAC samples were determined by UHPLC-MS/MS and CMIA, and the agreement of the two methods was evaluated by Bland-Altman plot. The calibration range of UHPLC-MS/MS method was 5 to 2000 ng/mL for CsA and 0.2 to 80 ng/mL for TAC. The inaccuracy and imprecision were -13.33% to 11.80% and <11.74% for CsA and -8.94% to 6.53% and <10.84% for TAC, respectively. Evaluated by Bland-Altman plot, the mean overestimation of CMIA compared to UHPLC-MS/MS was 53.7% for CsA and 48.1% for TAC.