Cucurbit[7]uril‐Dimethyllysine Recognition in a Model Protein

Here, we provide the first structural characterization of host–guest complexation between cucurbit[7]uril ( Q7 ) and dimethyllysine (KMe₂) in a model protein. Binding was dominated by complete encapsulation of the dimethylammonium functional group. While selectivity for the most sterically accessible dimethyllysine was observed both in solution and in the solid state, three different modes of Q7 ‐KMe₂ complexation were revealed by X‐ray crystallography. The crystal structures revealed also entrapped water molecules that solvated the ammonium group within the Q7 cavity. Remarkable Q7 ‐protein assemblies, including inter‐locked octahedral cages that comprise 24 protein trimers, occurred in the solid state. Cucurbituril clusters appear to be responsible for these assemblies, suggesting a strategy to generate controlled protein architectures.     

Chiral guest in a chiral framework: X-ray diffraction study

The inclusion compound of zinc lactate terephthalate with R-butan-2-ol, [Zn₂(R-Bu^sOH) (bdc)(S-lac)]?(R-Bu^sOH) (Bu^sOH is butan-2-ol, H₂bdc is terephthalic acid, S-H₂lac is lactic acid), was prepared by soaking crystals of [Zn₂(dmf)(bdc)(S-lac)]?DMF in pure R-butan-2-ol. The positions of chiral alcohol molecules in voids of the chiral framework and the host–guest contacts were determined by X-ray diffraction. These data provide an explanation for the origin of chiral discrimination of zinc lactate terephthalate toward the R-isomer of butan-2-ol.     

Applicability Evaluation of Bright Green‐Emitting Carbon Dots in the Solid State for White Light‐Emitting Diodes

Self‐quenching‐resistant and bright green‐emitting carbon dots (CDs) in the solid state were synthesized via a facile hydrothermal method. Their structure, optical properties together with their thermal and photostabilities, as well as their applicability in white LEDs were investigated. The obtained CDs have nearly spherical shape with a size around 4–5 nm. The resulting powder CDs show excitation‐independent emission behavior, and can be excited over a broad range from 300–450 nm. Under optimal excitation at 400 nm, the resultant powder CDs yield bright and broad green emission around 505 nm with full width at half maximum (FWHM) of about 110 nm and under 360 nm excitation with lifetime of 15.8 ns. A potential application of the green‐emitting CDs was evaluated by constructing a white light‐emitting diode lamp. The fabricated white LED lamp emitted bright, warm white light with excellent color rendering properties (a color rendering index of 86.9 and a correlated color temperature of 3863 K).     

Determination of Cadmium in Human Serum and Blood Samples after Dispersive Liquid–Liquid Microextraction Using a Task-Specific Ionic Liquid

Task-specific ionic liquid dispersive liquid–liquid microextraction (TSIL-DLLME) is a simple and rapid preconcentration approach for the measurement of cadmium in serum and blood samples of human subjects. In this method a novel task-specific ionic liquid, trioctylmethyl ammonium thiosalicylate (TOMATS), which has dual characteristics as a chelating agent and extractive solvent, was investigated. TOMATS complexes with Cd due to the chelating effect of the ortho-positioned carboxylate relative to the thiol functionality. The assessment of the optimum values of variables including the pH, amount of reagents (TOMATS, diluents, Triton X114, and back extracting acid solution), temperature, and incubation time, which affect the recoveries of analyte by TSIL-DLLME method were studied. After enrichment experiments, acidic solution was used to back extract the metal ions from the ionic liquid rich phase and with determination by electrothermal atomic absorption spectrometry. Using the optimal experimental conditions, the limit of detection (3?s), precision (relative standard deviation), preconcentration, and enhancement factors of developed method for Cd were found to be 0.05?µg/L, greater than 5%, 62.5, and 52.8, respectively. To check the accuracy of the developed method, certified reference material of serum and blood were analyzed by the developed method, and the measured values of Cd were in good agreement with the certified values. The developed method was applied successfully to determine Cd in blood and serum samples of lymphatic cancer patients relative to healthy controls.     

Synthesis of γ-butyrolactone fused cyclooctene

The expeditious route for the synthesis of γ-butyrolactone fused cyclooctene starting from the γ-butyrolactone fused cyclopentane through bicyclo[4.2.1]nonan-9-one is reported. Retro-Dieckmann’s condensation of bicyclo[4.2.1]nonan-9-one in presence of sodium methoxide and methanol furnished γ-butyrolactone fused cyclooctene in good yield. Surprisingly, the stereochemistry of ring-junction of γ-butyrolactone fused cyclooctene is different from the γ-butyrolactone fused cyclopentane, and the position of new ester group, which were confirmed unambiguously by X-ray analysis.     

Microwave-assisted asymmetric ring opening of meso-epoxides with aromatic amines catalyzed by a Ti-S-(−)-BINOL complex

Catalytic asymmetric ring opening of cyclohexene oxide and meso-stilbene oxide with anilines was catalyzed by a Ti-(S)-(−)-BINOL complex to afford β-amino alcohols in high yield (up to 95%) and good enantioselectivities (ee up to 55%) under microwave irradiation. The reaction using a microwave was found to be 10 times faster than traditional oil-bath heating with retention of enantioselectivity.     

TLC Determination of Aliphatic Polyamines on Calcium Sulfate Layers

Biogenic polyamines are sensitive markers for various diseases including cancer. Polyamines are difficult to analyze by chromatography due to their high polarity and water-solubility so that derivatization is an essential step for their chromatographic analysis. Earlier studies have shown the efficacy of calcium sulfate (CaSO₄) as a TLC coating material for the separation of polar compounds. The aim of this study was to explore the potential of CaSO₄ for the analysis of aliphatic polyamines without derivatization. The TLC of six polyamines (ornithine, citrulline, putrescine, cadaverine, spermidine and spermine) was carried out on CaSO₄ and silica gel plates using 11 different mobile phases. The results showed that CaSO₄ is superior to silica for the separation of underivatized polyamines. The development time of the CaSO₄ plates was also about one-third shorter as compared to silica. Methanol was the only solvent to produce differential R _F values for the polyamines studied. Ornithine (R _F , 0–2) and citrulline (R _F , 1–3) were separated from cadaverine (R _F , 0.93), spermine (R _F , 0.85) and spermidine (R _F , 0.85). For quantitative analysis, the polyamines were eluted from the coating material scratched from the plate and the absorbance of the supernatant was measured at 550 nm. The limits of detection (LOD) and quantification (LOQ) were found to be 0.75 and 1.88 μg, respectively. The procedure was applied to the quantitative separation of polyamines in spiked human urine samples (12.5–50 μg). This is probably the first study reporting a TLC method for the separation of underivatized polyamines.