Acetylenedicarboxylate and In Situ Generated Chlorofumarate-Based Hafnium(IV)-Metal-Organic Frameworks: Synthesis, Structure, and Sorption Properties.

New acetylenedicarboxylate (ADC) and chlorofumarate (Fum-Cl) based hafnium-metal-organic frameworks have been synthesized by alternatively reacting acetylenedicarboxylic acid in DMF or water with appropriate hafnium salt, in the presence of acetic acid modulator. The two materials of respective ideal formulas [Hf6O4(OH)4(ADC)6] (Hf-HHU-1) and [Hf6O4(OH)4(Fum-Cl)6] (Hf-HHU-2) have been structurally characterized by powder X-ray diffraction to be UiO-66 isostructural, consisting of octahedral [Hf6O4(OH)4]12+ secondary building units each connected to other units by 12 ADC or Fum-Cl linkers into a microporous network with fcu topology. This structure was confirmed by Rietveld refinement. Hf-HHU-2 is formed by in situ hydrochlorination of acetylenedicarboxylic acid to chlorofumarate. Its presence has been determined by combined Raman spectroscopy, solid-state NMR, scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopies. Hf-HHU-1 and Hf-HHU-2 exhibit very high hydrophilicity as revealed by their water sorption profiles, meanwhile Hf-HHU-2 adsorbs CO2 with an isosteric heat of 39 kJ mol-1. Hf-HHU-2 also adsorbs molecular iodine vapor exclusively as polyiodide anions due to grafted chloro-functions on the pores surface. It has been observed that defective nanodomains with reo tolopology can be introduced in the structure of Hf-HHU-2 by variation of the linker to metal-salt molar ratio.

The Low Toxicity of Graphene Quantum Dots is Reflected by Marginal Gene Expression Changes of Primary Human Hematopoietic Stem Cells.

Graphene quantum dots (GQDs) are a promising next generation nanomaterial with manifold biomedical applications. For real world applications, comprehensive studies on their influence on the functionality of primary human cells are mandatory. Here, we report the effects of GQDs on the transcriptome of CD34+ hematopoietic stem cells after an incubation time of 36 hours. Of the 20 800 recorded gene expressions, only one, namely the selenoprotein W, 1, is changed by the GQDs in direct comparison to CD34+ hematopoietic stem cells cultivated without GQDs. Only a meta analysis reveals that the expression of 1171 genes is weakly affected, taking into account the more prominent changes just by the cell culture. Eight corresponding, weakly affected signaling pathways are identified, which include, but are not limited to, the triggering of apoptosis. These results suggest that GQDs with sizes in the range of a few nanometers hardly influence the CD34+ cells on the transcriptome level after 36 h of incubation, thereby demonstrating their high usability for in vivo studies, such as fluorescence labeling or delivery protocols, without strong effects on the functional status of the cells.

Near-infrared (NIR) surface-enhanced Raman spectroscopy (SERS) study of novel functional phenothiazines for potential use in dye sensitized solar cells (DSSC).

Phenothiazines are of potential use as dye sensitizers in Grätzel-type dye sensitized solar cells (DSSC). Plasmonic nanoparticles like gold nanoparticles can enhance the power conversion efficiency of these solar cells. In this work near-infrared surface-enhanced Raman spectroscopy (NIR-SERS) is used to investigate the interaction between six novel phenothiazine-merocyanine dyes containing the three different functional groups rhodanine, 1,3-indanedione and cyanoacylic acid with plasmonic nanomaterials, to decide if the incorporation of plasmonic nanoparticles could enhance the efficiency of a Grätzel-type solar cell. The studies were carried out in the solution state using spherical and rod-shaped gold nanostructures. With KCl induced agglomerated spherical gold nanoparticles, forming SERS hot spots, the results showed low detection limits between 0.1 µmol L-1 for rhodanine containing phenothiazine dyes, because of the formation of Au-S bonds and 3 µmol L-1 for cyanoacrylic acid containing dyes, which formed H-aggregates in the watery dispersion. Results with gold nanorods showed similar trends in the SERS measurements with lower limits of detection, because of a shielding effect from the strongly-bound surfactant. Additional fluorescence studies were carried out to determine if the incorporation of nanostructures leads to fluorescence quenching. Overall we conclude that the addition of gold nanoparticles to rhodanine and 1,3-indanedione containing phenothiazine merocyanine dyes could enhance their performance in Grätzel-type solar cells, because of their strong interactions with plasmonic nanoparticles.

Realizing the Potential of Acetylenedicarboxylate by Functionalization to Halofumarate in ZrIV Metal-Organic Frameworks.

A strategy was developed to obtain from acetylenedicarboxylic acid either an acetylenedicarboxylate-based ZrIV metal-organic framework (MOF) with fcu topology or a halo-functionalized-MOF-801 through in situ ligand hydrohalogenation. The new materials feature exceptionally high hydrophilicity and CO2 /H2 adsorption energetics. The acetylenedicarboxylate linker and its functionalizable triple-bond discloses its potential in the engineering of microporous materials with targeted properties.