1983 - XAFS AND NANOMATERIALS: EARLY BEGINNING

ANTONELLA BALERNAINFN-LNF DAFNE-LIGHT

X-ray Spectroscopy and Synchrotron Radiation in materials physics: past, present and future. Roma TRE, 29/11/2019

UNIVERSITY OF L’AQUILA DECEMBER 1982DETERMINAZIONE DELLA STRUTTURA DI PICCOLE

PARTICELLE DI METALLI NOBILI MEDIANTE LUCE DI SINCROTRONE

Thesis Advisor: Prof. Armando Reale - University of L’Aquila

Persons and Laboratories involved:

P. Picozzi and S. Santucci – Department of Physics, University of L’Aquila

E. Burattini and E. Bernieri - INFN-LNF PWA Synchrotron Radiation Facility (in 1982).

S. Mobilio - INFN-LNF PULS Synchrotron Radiation Facility (in 1982)

Study of the structure of noble metal nanoparticles using synchrotron radiation.

1983 AND….

• Synchrotron Radiation• XAFS• Nanomaterials

J. Schwinger Nobel Prize 1965 Classical Relativistic quantum field theory

1st gen. dedicated ring Tantalus I (USA) 1968

2nd gen. dedicated storage ring SRS (UK) 1981

Proof of concepts, tests of theories 1897-1946

First observation of synchrotron radiation 1947

Parasitic use of electro-synchrotrons 1961

General Electric Res. Lab. - 70 MeV Electro- Synchrotron ( N.Y. USA)

Storage rings development 1960s

ADA - B. Touschek - LNF

3rd gen. dedicated storage ring ESRF (France) 1994

4th gen. - LINAC based accelerators FELs

Brightness increase

3rd* gen. ultimate storage rings like MAX IV(Sweden) near future

Using accelerators built for HE physics

First accelerators

built for SR - BM

Accelerators built to optimize SR -ID

5th gen. – Advanced accelerator concepts

Synchrotron LightShort History and

1983

XAFS

1971

1981

NANOMATERIALS

A. Balerna et al. - Phys. Rev. B. 1985Early beginning

Only 27 References

1983 THESIS ON AU NANOPARTICLES

SAMPLE PREPARATION: LONG STORY

Mylar is the brand name for a special type of stretched polyester film, which is more generally known as BoPET

or biaxially-oriented polyethylene terephthalate. The BoPet film was developed by DuPont, Hoechst, and Imperial

Chemical Industries (ICI) in the 1950s.

Mylar was is used in space applications also as a protective coating.

University of L’Aquila

INFN-LNF ADONE AND XAFS MEASUREMENTS

ADONE INFN-LNF

PWA

PULSPWA-BX1

First results submitted: end of 1984First shell EXAFS data analysis

Contractions explained with amacroscopic liquid drop modelDR = contractionf = surface stressRb= bulk NN distanceD = nanoparticle diameter.

GOLD NANOPARTICLES AND XANES

FCC structure

The question if the structure is still FCC up tothe second and third shells can be clarifiedusing the XANES spectra.The two peaks labeled b and c are typical ofFCC structures.As the nanoparticle size decreases there is ashift to higher energies and a broadening ofthe XANES peak.The shift is due to a shortening of the latticeparameter; the broadening is a consequenceof the cluster size distribution in each sampleand of the different weight of the highershells contributions.

C. R. Natoli docet

A. Balerna et al. Phys. Rev. B. 1985

Still being cited…

2017

2016

2016

2016

RESULTS INCLUDINGSECOND SHELL ANALYSIS

First and second shell

analysis

FCC structure not icosahedral

1986 RESULTS ON THE DYNAMIC PROPERTIES AND DEBYE TEMPERATURES

Good agreement for Au Bulk

QD=165 K

Gold bulk: Debye T. - thermalbehaviour of the mean-squarerelative displacement (MSDR)of the central atom relative toits neighbours.

Gold nanoparticles: surfacemodes included. NN distancecontractions and the increasedDebye-Waller factors dependon the high surface to volumeratio.

!" # = !%"+0.65 &ℏ()*+,-

./ +

1,-

"2.

Using a new theoretical formula agreement with the experimental Debye Waller factors.

AFTER 1983…

NANOMATERIALS BECOMING MORE AND MORE IMPORTANT

NANOMATERIALS- Nanomaterials have attracted attention because of their unique physical, chemical, and mechanical properties that differ from those of bulk solids and molecules.

- Nanomaterials exhibit distinct size-dependent properties in the 1–100 nm range where quantum phenomena are involved.

- The very large surface area of nanomaterials is one of the reasons for their novel properties and the high surface-to-volume ratio results in high significant effects of surface properties on their structure.

- Intensive research is being done for the use of nanomaterials inmany applications such as energy storage, energy conversion,solar cells, pharmaceuticals and drug-delivery, life scienceapplications, optoelectronics, sensing and actuation nanosystems,catalysis, and composite materials.

NANO DATA – NANO TECHNOLOGY

KNOWLEDGE BASE

Number of organisations by country

Publications by Sector

https://nanodata.echa.europa.eu/index.php?r=site%2Fstat Health - 27.9% - 280526

https://euon.echa.europa.eu/general-information

EUON – European Union Observatory For Nanomaterials

MANY JOURNALS ON

NANOMATERIALS ALSO WITH HIGH IMPACT FACTORS

• Nature Nanotechnology• Nano Letters• Advanced Materials• Nano Today• ACS Nano• Advanced Functional Materials• Journal of Physical Chemistry

Letters Biomaterials• Small• Nano Research• Scripta Materialia• Nanoscale

NATURE NANOTECHNOLOGY

IS AN INTERDISCIPLINARY JOURNAL THAT PUBLISHES PAPERS OF THE HIGHEST QUALITY AND SIGNIFICANCE

IN ALL AREAS OF NANOSCIENCE AND NANOTECHNOLOGY.

FIRST NUMBER OCTOBER 2006

Research areas covered in the journal- Carbon nanotubes and fullerenes- Computational nanotechnology- Electronic properties and devices- Environmental, health and safety issues- Molecular machines and motors- Molecular self-assembly- Nanobiotechnology- Nanofluidics- Nanomagnetism and spintronics- Nanomaterials- Nanomedicine- Nanometrology and instrumentation- Nanoparticles- Nanosensors and other devices- NEMS- Organic–inorganic nanostructures- Photonic structures and devices- Quantum information- Structural properties- Surface patterning and imaging- Synthesis and processing

SOME VERY RECENT PAPERSNANOMATERIALS LIFE AND ENVIRONMENTAL SCIENCE

Nanoparticles promote in vivo breast cancer cell intravasation and extravasation by inducing endothelial leakinessF. Peng et al. Nature Nanotechnology 14, 279–286 (2019) While most cancer nanomedicine is designed to eliminate cancer, the nanomaterial per se can lead to the formation of micrometre-sized gaps in the bloodvessel endothelial walls. Nanomaterials-induced endothelial leakiness (NanoEL) might favour intravasation of surviving cancer cells into the surroundingvasculature and subsequently extravasation, accelerating metastasis. Here, we show that nanoparticles induce endothelial leakiness through disruption ofthe VE-cadherin–VE-cadherin homophilic interactions at the adherens junction. We show that intravenously injected titanium dioxide, silica and goldnanoparticles significantly accelerate both intravasation and extravasation of breast cancer cells in animal models, increasing the extent of existingmetastasis and promoting the appearance of new metastatic sites. Our results add to the understanding of the behaviour of nanoparticles in complexbiological systems. The potential for NanoEL needs to be taken into consideration when designing future nanomedicines, especially nanomedicine to treatcancer.

Soil mobility of synthetic and virus-based model nanopesticidesP. L. Chariou et al. Nature Nanotechnology May (2019)Large doses of chemical pesticides are required to achieve effective concentrations in the rhizosphere, which results in the accumulation of harmfulresidues. Precision farming is needed to improve the efficacy of pesticides, but also to avoid environmental pollution, and slow-release formulations basedon nanoparticles offer one solution. Here, we tested the mobility of synthetic and virus-based model nanopesticides by combining soil columnexperiments with computational modelling. We found that the tobacco mild green mosaic virus and cowpea mosaic virus penetrate soil to a depth of atleast 30 cm, and could therefore deliver nematicides to the rhizosphere, whereas the Physalis mosaic virus remains in the first 4 cm of soil and would bemore useful for the delivery of herbicides. Our experiments confirm that plant viruses are superior to synthetic mesoporous silica nanoparticles andpoly(lactic-co-glycolic acid) for the delivery and controlled release of pesticides, and could be developed as the next generation of pesticide deliverysystems.

Medical applications

Environment applications

DIRECT OBSERVATION OF PICOSECOND

MELTING AND DISINTEGRATION OF

METALLIC NANOPARTICLESDespite more than a century of study, the fundamentalmechanisms behind solid melting remain elusive at thenanoscale. Ultrafast phenomena in materials irradiated

by intense femtosecond laser pulses have revived the

interest in unveiling the puzzling processes of melting

transitions. However, direct experimental validation ofvarious microscopic models is limited due to the difficultyof imaging the internal structures of materialsundergoing ultrafast and irreversible transitions. Here weovercome this challenge through time-resolved single-

shot diffractive imaging using X-ray free electron laser

pulses. Images of single Au nanoparticles show

heterogeneous melting at the surface followed by

density fluctuation deep inside the particle, which isdirectionally correlated to the polarization of thepumping laser. Observation of this directionality links thenon-thermal electronic excitation to the thermal latticemelting, which is further verified by molecular dynamicssimulations. This work provides direct evidence to the

understanding of irreversible melting with an

unprecedented spatiotemporal resolution.

Yungok Ihm et al. Nature Comm. 10, 2411

(2019)

Ultrafast single-pulse pump-probe imaging experiments were carried out using the MAXIC

chamber BL3 SACLA. X-ray energy fixed to 5.5 keV

and the average pulse energy at the sample position is ~100 μJ.

Gold

nanoparticles

XFEL SACLA

CONTRIBUTIONS OF DISTINCT GOLD

SPECIES TO CATALYTIC REACTIVITY FOR

CARBON MONOXIDE OXIDATION

Small-size (< 5 nm) gold nanostructures supported on reducible

metal oxides have been widely investigated because of the unique

catalytic properties they exhibit in diverse redox reactions.However, arguments about the nature of the gold active site havecontinued for two decades, due to the lack of comparable catalystsystems with specific gold species, as well as the scarcity of directexperimental evidence for the reaction mechanism under realisticworking conditions. The determination of the contribution of single

atoms, clusters and particles to the oxidation of carbon monoxide atroom temperature, by the aid of in situ XAFS analysis. The metallicgold component in clusters or particles plays a much more critical roleas the active site than the cationic single-atom gold species for theroom-temperature carbon monoxide oxidation reaction.

Li-Wen Guo et al. Nature Comm. 2016

DOI: 10.1038/ncomms13481

Gold nanoparticles used as catalysts.

The in situ experiments were conducted at the X18B beamlineof the National Synchrotron Light Source at Brookhaven

National Laboratory, operated at 2.8 GeV

WHAT ABOUT US….

AU BULK 1983 - 2009

1983 - Au BulkADONE LNF

2009 - Au BulkGILDA/LISA ESRF

EXAFS data up to 20 Å-1, analysis up to the Vth coordination shell.

doi: 10.1088/0953-8984/21/32/325404

Thermal dependent anharmonicity effects on gold bulk.

2008 CHANGES IN THE THERMAL BEHAVIOUR OF SMALL NANOPARTICLES AS A FUNCTION

OF SIZE DECREASE

Au-NP3 Au+Mylar D= 40 ÅAu-NP4 Au+Mylar D= 28 Å

Crossover from an initial thermal expansion to athermal contraction for the smaller nanoparticles.

STUDIES ON GOLD NANOPARTICLES NEVER ENDING

STORY….

WHEN YOU START YOU CANNOT STOP… STUDIES ON GOLD NANOPARTICLES ARE

STILL GOING ON!

GOLD-SILVER CATALYSTS: EFFECT OF CATALYST STRUCTURE ON THESELECTIVITY OF GLYCEROL OXIDATION

J. OF CATALYSIS 368, 324-335 (2018)

UNRAVELING THE ROLE OF HYBRID AU-CUO BIMETALLIC NANOPARTICLES AND THEIR STRUCTURAL FEATURES FOR SELECTIVE BENZYL ALCOHOL OXIDATION,

J. PHYS. CHEM. C 123, 2864-2871 (2019)

CONCLUSIONS- This adventure with Gold nanoparticles started at the end of

1982 with a visit at the Frascati National Laboratory.

- 1983 was the "hands on” year concluded with my Degree inPhysics.

- Due to their applications in many different fields in the lastdecades there has been a huge increase of studies onnanoparticles.

- I must thank many persons but surely among them Settimiofor his help during my Thesis but also for all the XAFSworks we have done together in a very interesting,intriguing and promising field like the structuralcharacterization of nanomaterials.

MANY THANKS TO SETTIMIOAND

THANK YOU FOR YOUR ATTENTION