Congrats to Magda Bonarowska on publishing the following work in the ECS Journal of Solid State Science and Technology:

Capacitance Properties of Chemically Prepared Carbon Nanostructure/Polyazulene Composites

Emilia Grądzka, Gian Andrea Rizzi, Magdalena Bonarowska and Piotr Dłużewski

Abstract
This work describes the chemical formation of composites based on different carbon nanostructures, such as single-walled carbon nanotubes, multi-walled carbon nanotubes, single-layer graphene oxide and p-type conducting polyazulene. The composite materials were synthesized in ethanol solution containing an appropriate amount of carbon nanostructures, azulene and ferric chloride as an oxidizing agent. The main attention was given to the electrochemical properties of these materials and their capacitance performance. The type of nanostructures influenced the morphology of the synthesized polyazulene. Thus, the relationship between the type of nanostructures present in the composite and its morphology and the electrochemical and stability properties were studied. The highest specific capacitance of 649 F g-1 was obtained for the SWCNT/PAZ composite. This value is nine times higher than the specific capacitance of pristine polyazulene synthesized under the same conditions. The SLGO/PAZ composite exhibited the lowest specific capacitance of 53 F g-1. However, this value was improved by approximately 77% by thermal treatment of the composite material at high temperature, resulting in an increase in the BET surface area as well as an increase in conductivity after heat treatment.

Congratulations to Gosia! Her paper entitled “Synthesis and Structure of Novel Copper(II) Complexes with N,O- or N,N-Donors as Radical Scavengers and a Functional Model of the Active Sites in Metalloenzymes” was published in the International Journal of Molecular Sciences. Congratulations!

https://www.mdpi.com/1422-0067/22/14/7286

To evaluate the antioxidant activity of potential synthetic enzyme mimetics, we prepared new five copper(II) complexes via a self-assembly method and named them [Cu(2-(HOCH₂)py)₃](ClO₄)₂ (1), [Cu(2-(HOCH₂)py)₂(H₂O)₂]SiF₆ (2), [Cu₂(2-(HOCH₂CH₂)py)₂(2-(OCH₂CH₂)py)₂](ClO₄)₂ (3), [Cu(pyBIm)₃](BF₄)₂·1.5H₂O (4) and [Cu(py₂C(OH)₂)₂](ClO₄)₂ (5). The synthetic protocol involved N,O- or N,N-donors: 2-(hydroxymethyl)pyridine (2-(HOCH₂)py), 2-(hydroxyethyl)pyridine (2-(HOCH₂CH₂)py), 2-(2-pyridyl)benzimidazole (pyBIm), di(2-pyridyl)ketone (py₂CO). The obtained Cu(II) complexes were fully characterised by elemental analysis, FTIR, EPR, UV-Vis, single-crystal X-ray diffraction and Hirshfeld surface analysis. Crystallographic and spectroscopic analyses confirmed chromophores of both monomeric ({CuN₃O₃} (1), {CuN₂O₄} (2), {CuN₆} (4), {CuN₄O₂} (5)) and dimeric complex ({CuN₂O₃} (3)). Most of the obtained species possessed a distorted octahedral environment, except dimer 3, which consisted of two copper centres with square pyramidal geometries. The water-soluble compounds (1, 3 and 5) were selected for biological testing. The results of the study revealed that complex 1 in solutions displayed better radical scavenging activity than complexes 3, 5 and free ligands. Therefore, complex 1 has been selected for further studies to test its activity as an enzyme mimetic. The chosen compound was tested on the erythrocyte lysate of two groups of patients after undergoing chemotherapy and chemoradiotherapy. The effect of the tested compound (1) on enzyme activity levels (TAS, SOD and CAT) suggests that the selected complex can be treated as a functional mimetic of the enzymes.

We are happy to anounce that our project entitled “Combined experimental and theoretical studies of the catalytic activity of RPE65 enzyme using biomimetic active centre models (CatVis)” (PI: A. Kubas) received funding under National Science Centre Opus 20 call (ca. 690 kPLN / 150 kEUR).

Adam’s milestone paper on electronic couplings dependency on spin states has just been published in the Journal of Chemical Theory and Computation: “How the Donor/Acceptor Spin States Affect the Electronic Couplings in Molecular Charge-Transfer Processes?”

Abstract:

The electronic coupling matrix element H_AB is an essential ingredient of most electron-transfer theories. H_AB depends on the overlap between donor and acceptor wave functions and is affected by the involved states’ spin. We classify the spin-state effects into three categories: orbital occupation, spin-dependent electron density, and density delocalization. The orbital occupancy reflects the diverse chemical nature and reactivity of the spin states of interest. The effect of spin-dependent density is related to a more compact electron density cloud at lower spin states due to decreased exchange interactions between electrons. Density delocalization is strongly connected with the covalency concept that increases the spatial extent of the diabatic state’s electron density in specific directions. We illustrate these effects with high-level ab initio calculations on model direct donor–acceptor systems relevant to metal oxide materials and biological electron transfer. Obtained results can be used to benchmark existing methods for H_AB calculations in complicated cases such as spin-crossover materials or antiferromagnetically coupled systems.

Read it online free:

https://pubs.acs.org/doi/10.1021/acs.jctc.1c00126

Our paper “Lerf–Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins” is online! This is excellent collaboration between CoopCat team, AMU team in Poznan and WUT in Warsaw.

Abstract:

Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf–Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO and RGO and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states’ density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.

Check online:

https://www.nature.com/articles/s41598-021-86880-1

We look for potential candidates for Post-Doc application under the PASIFIC programme coordinated by the Polish Academy of Sciences. Check more details in the JOBS section.

Happy to inform that Magda’s work on tetrachloromethane hydrodechlorination is out online! Check:

Bonarowska, M.; Kaszkur, Z.; Matus, K.; Drelinkiewicz, A.; Szumełda, T.; Kubas, A.
Towards High Efficacy of Pd-Au/C Catalyst for Tetrachloromethane Hydrodechlorination.
Chemistry 2021, 3, 338-359. https://doi.org/10.3390/chemistry3010025

Our work done in collaboration with the group of Prof. JC Colmenares is out. Check how we used H-terminated clusters to get insights into chemical transformations of HMF at the TiO2(atanase) surface. Our approach involve state-of-the-art DLNO-CCSD(T) energy calculations and numerical partial Hessian evaluation for reliable IR and Raman spectra prediction.

“Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran by Visible Light‐Driven Photocatalysis over In Situ Substrate‐Sensitized Titania”

A. Khan, M. Goepel, A. Kubas, D. Łomot, W. Lisowski, D. Lisovytsky, A. Nowicka, J.C. Colmenares, R. Glaser
ChemSusChem, 2021, https://doi.org/10.1002/cssc.202002687

Boosting the Performance of Nano-Ni Catalysts by Palladium Doping in Flow Hydrogenation of Sulcatone

Catalysts 2020, 10(11), 1267

The effect of Pd doping on nano-Ni catalyst hydrogenation aptitude in sulcatone (6-methyl-5-hepten-2-one) hydrogenation was investigated. Obtained results demonstrated that the addition of non-catalytic amounts of Pd to the surface of parent Ni catalyst improves the activity to the extent that it surpassed the activity of 2.16 wt% Pd catalyst (model catalyst) at optimal reaction conditions in the flow hydrogenation of an unsaturated ketone. Pd doping improves hydrogen activation on the catalyst, which was found to be a rate-limiting step using kinetic isotopic measurements and theoretical calculations.

It is my pleasure to invite you to an online seminar of the Cooperative Catalysis Group. Tomorrow, on Friday, our guest will be the recipient of this year’s NCN scientific prize dr hab. Michał Tomza from the Faculty of Physics of the University of Warsaw.

Below please find the Zoom link and talk details.

Time: Oct 30, 2020 11:00 AM Warsaw
https://zoom.us/j/96570388483?pwd=c1BTV3pZcktTU0tUbmtEdFB0ejJUUT09
Meeting ID: 965 7038 8483
Passcode: 336789

Talk title: “Accurate ab initio quantum-chemical calculations for ultracold scattering experiments”

Abstract:
Hybrid systems of laser-cooled trapped ions and ultracold atoms combined in a single experimental setup have recently emerged as a new platform for fundamental research in quantum physics and chemistry [1]. Reaching the ultracold s-wave quantum regime has been one of the most critical challenges in this field for a long time. Unfortunately, the lowest attainable temperatures in experiments using the Paul ion trap are limited by the possible rf-field-induced heating related to the micromotion [2]. Recently, buffer gas cooling of a single ion in a Paul trap to the quantum regime of ion-atom collisions was realized, and a deviation from classical Langevin theory was observed by studying the spin-exchange dynamics, indicating quantum effects in the ion-atom collisions [3]. In my seminar, I will present how quantum chemical calculations of electronic structure and scattering dynamics can guide and explain quantum physics and chemistry experiments. In particular, I will describe how, in collaboration with experimental groups from Amsterdam [3], Stuttgart [4], and Freiburg, we have overcome the micromotion limitation. I will also discuss incoming applications, including first observation and application of magnetic Feshbach resonances, to control ultracold ion-atom collisions.

[1] Tomza et al, Rev. Mod. Phys. 91, 035001 (2019)
[2] Cetina et al., Phys. Rev. Lett. 109, 253201 (2012)
[3] Feldker et al, Nature Phys. 16, 413 (2020)
[4] Schmid et al, Phys. Rev. Lett. 120, 153401 (2018)