Analytical Chemistry

Prof. Paolo Pastore (paolo.pastore@unipd.it); prof. Denis Badocco (denis.badocco@unipd.it); prof. Sara Bogialli (sara.bogialli@unipd.it); dr. Luca Cappellin (luca.cappellin@unipd.it); prof. Valerio Di Marco (valerio.dimarco@unipd.it); dr. Gabriella Favaro (gabriella.favaro@unipd.it); prof. Marco Frasconi (marco.frasconi@unipd.it); prof. Andrea Tapparo (andrea.tapparo@unipd.it); dr. Marco Roverso (marco.roverso@unipd.it); dr. Alessandra Zanut (alessandra.zanut@unipd.it); dr. Fazel Abdolahpur Monikh (fazel.monikh@unipd.it).

 

The Analytical Chemistry Laboratories are equipped with a range of advanced instruments, such as high-resolution LC-MS (Q-Exactive by Thermo), ICP-MS (Agilent), GC-MS/MS (Thermo), and several others. These instruments are dedicated to various research lines, including:

• emerging contaminants in the environment and food;
• atmospheric chemistry;
• metal-ligand complexation in aqueous solutions for pharmaceuticals;
• applied analytical chemistry;
• optical and electrochemical sensors;
• nanostructured materials for sensing and organ-on-chips applications;
  

Within the group, a special focus lies on safe-by-design advanced materials, investigating adverse effects of nanomaterials on the environment and human health. This includes developing analytical methods for understanding nanomaterial behavior, exploring interactions with biological components, tracing nanomaterial movement in organisms, and applying them for environmental remediation and risk assessment.

 Selected publications:

• An analytical workflow for dynamic characterization and quantification of metal-bearing nanomaterials in biological matrices.Nat Protoc 17, 1926–1952 (2022);
• Porous hydrogel scaffolds integrating Prussian Blue nanoparticles: a versatile strategy for electrochemical (bio)sensing, Sensors and Actuators B: Chemical 2023, 376, 132985;
• Chelation of Theranostic Copper Radioisotopes with S-Rich Macrocycles: From Radiolabelling of Copper-64 to In Vivo Investigation. Molecules 2022, 27, 4158;
• Exploring volatile organic compound emission from thermally modified wood by PTR-ToF-MS, Analyst, 2022,147, 5138-5148;
• Metallic functionalization of magnetic nanoparticles enhances the selective removal of Glyphosate, AMPA, and Glufosinate from surface water, Environmental Science: Nano, 2023, Just accepted paper;

 

group website

  EPR Spectroscopy

Prof. Donatella Carbonera (donatella.carbonera@unipd.it); Prof. Marilena Di Valentin (marilena.divalentin@unipd.it); Prof. Antonio Toffoletti (antonio.toffoletti@unipd.it); Prof. Lorenzo Franco (lorenzo.franco@unipd.it); Prof. Marco Ruzzi (marco.ruzzi@unipd.it); Dr. Alfonso Zoleo (alfonso.zoleo@unipd.it); Dr. Antonio Barbon (antonio.barbon@unipd.it); Dr. Marco Bortolus (marco.bortolus@unipd.it): Dr. Gabriele Stevanato (gabriele.stevanato@unipd.it).

The research activity of the group is focused on the development and application of Electron Paramagnetic Resonance (EPR) techniques to Material Science (graphene, metal nanoparticles, organic photovoltaics, cultural heritage materials), and Biology (natural and artificial photosynthetic systems, hydrogenases and bio-inspired analogs for the bio-production of hydrogen, protein dynamics as detected by spin labelling techniques).
The facilities of the EPR Laboratory include the following spectrometers:

• X/Q-band EPR with CW, pulsed, ENDOR, PELDOR and time-resolved accessories
• X-band EPR with CW, pulsed, ENDOR, and time-resolved accessories
• X-band CW-EPR for routine experiments
• X-band time-resolved EPR for analysis of light-induced processes
• Optically detected Magnetic Resonance (ODMR).
• UV-Vis.

We also have available an FPLC for protein purification

 

1. Altering the exciton landscape by removal of specific chlorophylls in monomeric LHCII provides information on the sites of triplet formation and quenching by means of ODMR and EPR spectroscopies, BBA Bioenerg., 2021, 1862, 148481.
2. Orientation-Selective and Frequency-Correlated Light-Induced Pulsed Dipolar Spectroscopy, J. Chem. Phys. Lett., 2021, 12, 3819 - 3826.
3. Spin–Orbit Charge-Transfer Intersystem Crossing of Compact Naphthalenediimide-Carbazole Electron-Donor–Acceptor Triads, J. Phys. Chem. B, 2021, 125, 10813 - 10831.
4. Understanding and controlling the efficiency of Au24M(SR)18 nanoclusters as singlet-oxygen photosensitizers, Chem. Sci., 2020, 11, 3427 - 3440.
5. Quantification of Photophysical Processes in All-Polymer Bulk Heterojunction Solar Cells, Sol. RRL, 2020, 4, 2000181.

group website

Updated  May 6^th, 2022

• EPR Spectroscopy Download

  Electrocatalysis and Applied Electrochemistry

 Prof. Abdirisak Ahmed Isse (abdirisak.ahmedisse@unipd.it); Prof. Christian Durante (christian.durante@unipd.it); Dr. Marco Fantin (marco.fantin@unipd.it)

The research group applies electrochemical methods to study chemical problems in various fields such as electrochemical surface treatment, (electro)catalysis, and environmental electrochemistry. The research activity is centered in molecular electrochemistry with particular attention to the study of mechanisms of electrochemical processes, the development of eco-friendly electrosynthesis and electrocatalytic materials and/or electrocatalytic processes. The main topics of research activity of the group are:

-Development of electrocatalytic materials

-Electrochemical activation of small molecules

-Electrochemical approaches to controlled radical polymerization

-Electrochemical surface treatment (electropolishing, electrodeposition)

 

Daniel, G.; Zhang, Y.; Lanzalaco, S.; Brombin, F.; Kosmala, T.; Granozzi, G.; Wang, A.; Brillas, E.; Sirés, I.; Durante, C. Chitosan-derived nitrogen-doped carbon electrocatalyst for a sustainable upgrade of oxygen reduction to hydrogen peroxide in UV-assisted electro-fenton water treatment. ACS Sustain. Chem. Eng. 2020, 8, 14425–14440.

• Lorandi, F.; Fantin, M.; Wang, Y.; Isse, A.A.; Gennaro, A.; Matyjaszewski, K. Atom transfer radical polymerization of acrylic and methacrylic acids: preparation of acidic polymers with various architectures, ACS Macro Letters, 2020, 9, 693-699.
• Mazzucato, M.; Daniel, G.; Mehmood, A.; Kosmala, T.; Granozzi, G.; Kucernak, A.; Durante, C. Effects of the induced micro- and mesoporosity on the single site density and turn over frequency of Fe-N-C carbon electrodes for the oxygen reduction reaction. Appl. Catal. B Environ. 2021, 291, 120068–120083.
• Grecchi, S.; Arnaboldi, S.; Isse, A.A.; D’Aloi, C.; Gennaro, A.; Mussini, P.R. Electrocatalytic reduction of bromothiophenes vs bromobenzenes on gold and silver electrodes: enhancement from S specific adsorption and modulation from substituent effects, Electrochim. Acta, 2022, 403, 139563

 

group website

updated April 26th, 2022

• Electrocatalysis and Applied Electrochemistry 2022 Download

  Hybrid molecules and materials - HyMolMat

The research activities of the group are focused on the design, synthesis, and characterization of hybrid organic-inorganic compounds:

1. Metal complexes and molecular compounds are developed for applications in biomimetic catalysis and nanomedicine. Specifically, polyoxometalates (tungstates, molybdates, and vanadates) are functionalized with peptides or other organic moieties to confer recognition capabilities towards biological targets. Spectroscopic techniques (NMR, FT-IR, UV-vis, fluorimetry, circular dichroism), cyclic voltammetry, and dynamic light scattering are employed to investigate the behavior of these compounds in solution.

2. Composite materials incorporating nanomaterials (such as halloysite nanotubes, nanocellulose, and metal-organic frameworks) within polymeric matrices are developed. Whenever possible, starting materials are sourced from waste materials (e.g., textiles). These novel materials are functionalized with catalytic units to foster green chemical transformations. Electron microscopies (TEM, SEM), Thermal characterizations (TGA, DSC), surface analysis (XRD, Raman, Z-potential) are applied for their characterization, while HPLC, GC, NMR are used to monitor their activity.

References

1) Bortolus, M., Kotynia, A., Saielli, G., Ruzza, P., Di Valentin, M., Carraro, M., Brasuń, J. Detailed investigation of the binding abilities of the heterodomain of a multiHis cyclopeptide toward Cu(II) ions (2024) J. Pept. Sci. DOI: 10.1002/psc.3568
2) Yu, J., Boudjelida, S., Galiano, F., Figoli, A., Bonchio, M., Carraro, M.Porous Polymeric Membranes Doped with Halloysite Nanotubes and Oxygenic Polyoxometalates (2022) Adv. Mater. Interf., 9 (11), art. no. 2102152.
3) Yu, J., Niedenthal, W., Smarsly, B.M., Natile, M.M., Huang, Y., Carraro, M. Au nanoparticles supported on piranha etched halloysite nanotubes for highly efficient heterogeneous catalysis (2021) Appl. Surf. Sci., 546, art. no. 149100.
4) Tagliavini, V., Honisch, C., Serratì, S., Azzariti, A., Bonchio, M., Ruzza, P., Carraro, Enhancing the biological activity of polyoxometalate-peptide nano-fibrils by spacer design (2021) RSC Adv., 11 (9), pp. 4952-4957.

  Molecular Electrochemistry and Nanosystems

Flavio Maran (flavio.maran@unipd.it); Sabrina Antonello (sabrina.antonello@unipd.it); Sara Bonacchi (sara.bonacchi@unipd.it), Abhijit Nag (abhijit.nag@unipd.it)

The M.E.N. Group focuses on molecular aspects of electrochemical reactions and nanosystems, from both fundamental and applied viewpoints. Specific research topics include:
-    Electron transfer through molecular bridges and interfaces;
-    Dissociative electron transfer;
-    Monolayer-protected clusters: electrochemical, optical and magnetic properties, redox catalysis, drug-delivery systems;
-    Electrochemical sensors for cancer biomarkers and volatile chemicals;
-    Self-assembled monolayers of conformationally constrained peptides.
The M.E.N. group is equipped with state-of-the-art electrochemical instrumentations, including electrogenerated chemiluminescence and SECM, STM and AFM, PM-IRRAS and UV-visible spectrometers, HPLC.

-    Electrocrystallization of Monolayer Protected Gold Clusters: Opening the Door to Quality, Quantity and New Structures, J. Am. Chem. Soc., 2017, 139, 4168-4175.
-    Magnetic Ordering in Gold Nanoclusters, ACS Omega, 2017, 2, 2607-2917.
-    From Blue to Green: Fine Tuning of Photoluminescence and Electrochemiluminescence in Bifunctional Organic Dyes, J. Am. Chem. Soc., 2017, 139, 2060-2069.
-    Molecular Electrochemistry of Monolayer-Protected Clusters, Curr. Opinion Electrochem., 2017, 2, 18-25.
-    A Magnetic Look into the Protecting layer of Au25 Clusters, Chem. Sci., 2016, 7, 6910-6918.

group website

• Molecular Electrochemistry and Nanosystems Download

  Nano & Molecular Catalysis

Marcella Bonchio (marcella.bonchio@unipd.it); Mauro Carraro
(mauro.carraro@unipd.it); Andrea Sartorel (andrea.sartorel@unipd.it); Luca
Dell’Amico (luca.dellamico@unipd.it); Giacomo Saielli (giacomo.saielli@unipd.it); Paolo Costa (paolo.costa@unipd.it); Francesco Rigodanza (francesco.rigodanza@unipd.it); Daniele Mazzarella (daniele.mazzarella@unipd.it); Giulio Goti (giulio.goti@unipd.it); Katy Elizabeth Medrano Uribe (katyelizabeth.medranouribe@unipd.it);

The group has established a highly interdisciplinary activity on the study of novel bio-inspired catalytic systems, molecular materials and functional hybrid architectures. Main topics include: (i) artificial photosynthesis: development of multi-redox routines powered by light irradiation for water splitting, CO2 fixation and stereoselective light-driven reactions for the synthesis of biologically relevant molecules with application to flow photochemistry; (ii) design of synthetic enzymes (synzymes), bio-conjugate nanomaterials and hybrid membranes for the interaction with diverse biological targets involved in ROS-related diseases, with applications in catalysis and nanomedicine; (iii) computational modeling in collaboration with ITM-CNR: DFT calculations of spectroscopic properties of organic and organometallic systems and MD simulations of ionic liquids and ionic liquid crystals.

-    Hydrogen Evolution by FeIII Molecular Electrocatalysts Interconverting between Mono and Di-Nuclear Structures in Aqueous Phase, ChemSusChem, 2017, 10, 4430–4435.
-    Photo-assisted water oxidation by high-nuclearity cobalt-oxo cores: tracing the catalyst fate during oxygen evolution turnover, Green Chem., 2017, 19, 2416-2426.
-    Merged Heme and Non-Heme Manganese Cofactors for a Dual Antioxidant Surveillance in Photosynthetic Organisms, ACS Catal., 2017, 7, 1971-1976.
-    Tuning Iridium Photocatalysts and Light Irradiation for Enhanced CO2 reduction, ACS Catal., 2017, 7, 154-160.
-    Dynamic Anti-Fouling of Catalytic Pores Armed with Oxygenic Polyoxometalates, Adv. Mater. Interfaces, 2015, 2, 1500034-1500034.

group website

• Nano & Molecular Catalysis Download

  Nanostructures & Optics

Prof. Moreno Meneghetti (moreno.meneghetti@unipd.it); dr. Lucio Litti (lucio.litti@unipd.it)

Research activities at NOL are on the synthesis, characterization, modelling and applications of nanostructures in nanobiotechnology and related fields and for new nanomaterials for solar energy conversion (photovoltaic and thermal) and cultural heritage. Nanostructures are usually obtained by laser ablation of bulk solids under solvents. Plasmonic properties of metal nanoparticles are exploited in particular for the SERS (surface enhanced Raman scattering) effect, whereas the magnetic properties for magnetophoresis. Finite element based simulations are used to model the optical responses of complex nanostructured assemblies. For the nanobiotechnology field the SERS technique is used for applications like tumor cell targeting and identification, functionalizing plasmonic and magneto-plasmonic nanostructures with antibodies and engineered peptides. Nanobiotechnology, but also environmental applications are developed also using µfluidic devices to be integrated in new portable sensor technologies. Raman and SERS  nanostructures are exploited  also in cultural heritage studies for the identification of pigments, dyes, and other organic materials present in artworks.

- Predictions on the SERS enhancement factor of gold nanosphere aggregate samples, Physical Chemistry Chemical Physics, 2019, 21, 15515 – 15522.
- A surface enhanced Raman scattering based colloid nanosensor for developing therapeutic drug monitoring, Journal of Colloid and Interface Science, 2019, 533, 621 – 626.
- Safe core-satellite magneto-plasmonic nanostructures for efficient targeting and photothermal treatment of tumor cells, Nanoscale, 2018, 10, 976–984.
- Enhanced EGFR Targeting Activity of Plasmonic Nanostructures with Engineered GE11 Peptide, Adv. Healthcare Mater., 2017, 6, 1700596.
- High-Quality, Ligands-Free, Mixed-Halide Perovskite Nanocrystals Inks for Optoelectronic applications, Advanced Energy Material, 2017, 7, 1601703.

group website

updated 1^st October 2019

  Synthetic Photocatalysis, Design and Mechanisms

The research group interests spans within the fields of organic synthesis and catalysis, and photochemistry. We solve complex synthetic problems in a sustainable manner, merging light with homogeneous/heterogeneous catalysis. Our main expertise include the design and synthesis of novel organic photocatalysts (J. Am. Chem. Soc. 2023, 145, 3, 1835–1846), well as the investigation of the reaction mechanism that allow access to previously unexplored reactivity (Chem. Sci. 2024, 15, 271). 

Prof. Luca Dell’Amico (luca@unipd.it); Dr Giulio Goti (giulio.goti@unipd.it); Dr Daniele
Mazzarella (daniele.mazzarella@unipd.it); Dr Katy Medrano
(katyelizabeth.medranouribe@unipd.it)

The activity of the group focuses on different research topics:
1) The design, synthesis, and characterization of novel organic
photocatalysts, and their utilization in innovative light-driven processes.
2) The development of novel sustainable synthetic methods, involving the
use of organocatalysis, photocatalysis, and flow chemistry to access
important biologically active compounds and key structural building
blocks.
3) The study and elucidation of complex light-driven transformations by
means of in-situ NMR, laser flash photolysis, as well as DFT analysis.
The group is supported by EU with the ERC Starting Grant SYNPHOCAT,
several MSCA Actions, PRIN and PNRR Young Researchers program.

1. “The Rational Design of Reducing Organophotoredox Catalysts Unlocks Proton-Coupled
Electron-Transfer and Atom Transfer Radical Polymerization Mechanisms” J. Am. Chem. Soc.
2023, 145, 1835–1846.
2. “Unveiling the impact of the light-source and steric factors on [2+2] heterocycloaddition
reactions” Nat. Synth., 2023, 2, 26–36.
3. “A General Organophotoredox Strategy to Difluoroalkyl Bicycloalkane (CF2-BCA) Hybrid
Bioisosteres” Angew. Chem. Int. Ed. 2023, 135, e2023035.
4. “A Rational Approach to Organo‐Photocatalysis. Novel Designs and Structure‐Property‐
Relationships” Angew. Chem. Int. Ed. 2021, 133, 1096-1111.
5. " Mechanisms and Synthetic Strategies in Visible-Light-Driven [2+2]-Heterocycloadditions "
Angew. Chem. Int. Edit., 2023, 62, e202217210.

Group Website: https://dellamicogroup.com/

• Synthetic Photocatalysis, Design and Mechanisms Group Download

  Wet Chemistry and Colloids Group

Prof. Silvia Gross (silvia.gross@unipd.it); Dr. Francesco Lamberti (francesco.lamberti@unipd.it)

The group research activities focus on metal oxocluster-reinforced organic-inorganic hybrid materials, low temperature hydrothermal synthesis of nanocrystalline transition metal oxides and sulphides in an aqueous environment, nucleation and growth from optimised colloidal suspensions, inorganic chemistry in a nanoreactor with room temperature miniemulsion approach to crystalline inorganic nanostructures, Crystallisation of small and monodispersed nanoparticles via microfluidics, surface chemistry and functionalisation, structural and spectroscopic characterisation of inorganic nanostructures and Structural and spectroscopic characterisation of inorganic nanostructures.

The laboratory facilites include two fully equipped laboratories for inorganic, molecular and colloidal synthesis

• Schlenk lines for the synthesis of highly air-sensitive inorganic and metalorganic compounds;
• A complete equipment for hydrothermal synthesis or the preparation of inorganic materials under non-conventional conditionsConventional Memmert UNE-400 for hydrothermal synthesis;
• Ball miller Retsch MM200 for the milling/grinding of samples and for mechanosynthesis, up to 60 Hz;
• Centrifuge Hermle Z366: Universal table top centrifuge;
• UV lamps Helios Italquartz 125 W and 400 W, for UV-activated reactions (e.g. polymerization processes);
• Sonicator Laborsonic P Sartorius Stedim ultrasonicator for the homogeneization of miniemulsions;
• Custom made spin, dip and spray coaters ror the deposition of inorganic and hybrid films and coatings;

The lab is also equipped with an ultrasonic spraying system that allows the fabrication of thin and uniform films for different applications. The spray gun can process both liquid and colloidal solutions creating micrometric drops on the surface. Furthermore, the deposition is performed in a dedicated climate chamber and, optionally, the sample can be heated up to 500 degrees by a precise titanium hotplate.

 

group website