A strategy was developed to obtain from acetylenedicarboxylic acid either an acetylenedicarboxylate-based Zr 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 CO /H adsorption energetics. The acetylenedicarboxylate linker and its functionalizable triple-bond discloses its potential in the engineering of microporous materials with targeted properties.

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.

Mercaptoacetate modulation represents an easy way of introducing thiol groups into UiO-MOFs for enhanced uptake of Ag+ from aqueous solutions.

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.

Surface halogenation is an important means to tune or improve functionalities of solid-state materials. However, this concept has been hardly explored and exploited in the engineering of metal-organic frameworks (MOFs). Here, a facile approach to obtain halo-functionalized derivatives of zirconium fumarate (MOF-801) is developed by reacting zirconium halides (ZrX4; X = Cl, Br, I) in water with acetylenedicarboxylic acid. The latter quantitatively undergoes an unusual in situ linker transformation into halofumarate via trans addition of HX to the −CC– triple bond. This HX addition and MOF formation happen in a one-pot reaction, that is, the in situ generated halogenated linker reacts with zirconium ions in solution to yield three microporous HHU-2-X MOFs (X = Cl, Br, I) with an fcu topology, containing UiO-type [Zr6O4(OH)4] secondary building units 12-fold connected by halofumarate linkers. The halogen (Cl) groups in HHU-2-Cl result in increased hydrophilicity for water vapor sorption as well as increased gas uptakes of 21% SO2, 24% CH4, 44% CO2, and 154% N2 when compared to the non-halogenated MOF-801. The tuning of the inner surface chemistry is realized to yield multipurpose adsorbent materials for enhanced gas and vapor uptakes over their non-halogenated analogues. The gas sorption properties of the chlorinated HHU-2-Cl material indicate its suitability for CO2, N2, and SO2 capture and separation, while its water sorption profile yields a high heat storage capacity of 500 kJ kg–1, making it promising for adsorption-based thermal batteries and dehumidification applications.