NanoRelease Task Group 1: Material Characteristics Characteristics Relevant to Uptake and Bioavailability 1

NanoRelease Task Group 1: Material Characteristics

Characteristics Relevant to Uptake and Bioavailability

1www.riskscience.org

http://www.riskscience.org/

TG1: Material CharacteristicsCHARGE

• Provide overview of physical and chemical attributes of nanoparticles that may affect their uptake in the alimentary tract.

• Provide overview of physical and chemical attributes of the food matrix that may affect nanoparticle uptake in the alimentary tract.



Task Group 1 Material Characteristics

Sub-Group 1 - What is (may be) in the food chain

Sub-Group 2 – Nanomaterial properties

Matrix interactions

relevant to uptake & bioaccessibility

Task Group 1: Sub-Groups



CHAIR Scott Thurmond US FDA

Tim Duncan US FDA

Greg Noonan US FDA (CFSAN)

Jeff Yourick US FDA (OARSA)

CHAIR Rickey Yada University of Guelph

CHAIR Neil Buck DSM Ltd

Gemma Janer Leitat Technological Center

Prabir Dutta Ohio State University

Jamie Oxley Southwest Research Institute

Cristina Sabliov Louisiana State University and LSU AgCenter

Iseult Lynch University College Dublin

Karen Tiede The (UK) Food & Environment Research Agency

Julian McClements University of Massachusetts

Chris DeMerlis ColorCon Inc.

Andy Rao Cornell Food Science

Michael Rogers Rutgers University

Mengshi Lin University of Missouri

Qingrong Huang Rutgers University

Qixin Zhong University of Tennessee

Yuan Yao Purdue University

TG1 MembersSub-Group 1: ‘Catalogue’ Sub-Group 2: ‘Particle Properties’


Additional involved members/advisors: Anil Patri (US NIH), Jun Jie Yin (US FDA), Kevin Powers (U. of Florida), Lekh Juneja (Taiyo Kagaku Co, Japan), Sean Linder (US FDA), Il Je Yu (Hoseo University, S. Korea), Jonathan Powell (MRC Human Nutrition Research)


Sub-Group 1: Catalogue

Purpose of the Nanomaterial Catalogue

• Review of ENM that are purportedly in internationally marketed food products • Provide “real time” input to NanoRelease task groups to support identification

and development of analytical detection and characterization methodson nanomaterials used in commerce.

Collection methods

Resources:• FoodEssentials LabelBase, Gladson Nutrition database, Mintel Global New

Products database• U. S. Patent and Trademark Office and European Patent Office databases• Project on Emerging Nanotechnologies consumer inventory• Published literature and business press• Threshold® professional literature/patent search firm• Regional sources



Sub-Group 1: CatalogueResults

Nanomaterial Products Origin

Calcium Primarily dairy/soy (e.g. yogurts, supplemented milk, etc.)

Various Asian countries

Silver Dietary supplements NA, Oceania

Titanium dioxide, silver, clay, ceramics

Food contact materials

NA, Europe, Asia

Nanocapsules (liposomes, micelles, cyclodextrin, etc.)

Dietary/nutritional supplements

NA, Europe

Mineral supplements

Various minerals (other than calcium)

NA, Asia,

Sub-Group 1: Catalogue

Summary• Catalogue is just a snapshot of what may be on the international market.• Two nanomaterials, calcium and silver, predominate, although nano-calcium was

found only in Asia.• Supplements (nutritional and dietary) dominate the product classes for the

incorporation of nanomaterials.

Conclusions

• Lack of labeling requirements in most countries make compilation of a comprehensive catalogue difficult.

• Although this snapshot is focused primarily on North America and Asia, we feel that it may be representative of food-related nanoproducts found in other regions of the world.

• Without analytical data for the identified nanoproducts, it is impossible to confirm that they contain nanomaterials.



Sub-Group 1: CatalogueNanoMaterials known to be present in the food chain



Sub-Group 2: Material Characteristics



Sub-Group 2: Material Characteristics

ParticlesMetals and metalloidsPolymeric encapsulates

Emulsions, Dispersions and Powders Thereof



Chou, L. Y. T, K. Ming and W. C. W. Chan. Chem. Soc. Rev. 2011, 40, 233-245.

General properties of interest



Mucus EpitheliumVasculature &

lymphatics Local tissues

Paracellular

Persorption

Transcellular

Nano Form Materials

Physical Change

Disruption to molecular components

Cytosis & accumulationSequestration &

eliminationDig

estiv

e Pr

oces

ses

& F

ood

Inte

racti

onSub-Group 2: Material Characteristics



Sub-Group 2: Material CharacteristicsMetals and Metalloids

Definition and Usage:• Metal and metalloid particles in food are used for a wide range of applications: nutrients, colour additives, flow agents, food contact materials. Their nano-size may be intentional (e.g., to improve functionality as in the absorption of nutrients) or unintentional (portion of a particle population above the nano range).

Requirements for Characterisation:• Concentration and chemical composition (core and surface)• Primary size (and surface are), shape, and aggregation/agglomeration/exfoliation state.• Surface charge

Uncertainties:• Most relevant concentration units• At which point NM should be characterized. Prior to inclusion in food matrix, in the food matrix, in contact with gastrointestinal fluids…



Sub-Group 2: Material CharacteristicsMetals and Metalloids

Analytical Gaps and Difficulties:• How to extract nanomaterials from food matrices without altering their properties, such as aggregation/agglomeration/exfoliation state.• Quantitative method for metal content exist (e.g., ICP-MS) but do not inform on the properties of the material (size, shape, surface coating).• Methods that allow the evaluation of size, shape, and aggregation state (e.g., TEM, RAMAN) are not quantitative, low throughput and expensive.

Matrix Interactions:• Food matrices may affect the properties (and ultimately uptake) of nanomaterials, by changing their aggregation/agglomeration/exfoliation state, by changing their surface properties (by coating them), and when considering relatively soluble nanomaterials by determining their dissolution rate into ions.

• Nanomaterials can also change the food matrix by modifying the bioavailability of some nutrients or chemically modifying them.



Sub-Group 2: Material CharacteristicsPolymeric Encapsulates

Definition and UsagePolymeric nanoparticles with a typical size range of 20-1000 nm formed by a polymeric core, with the active component entrapped in the polymeric matrix, usually surrounded by a surfactant layer that stabilizes the system.

Requirements for CharacterisationSize, zeta potential, morphology, hydrophobicity, solubility, stability, degradation

Analytical Gaps and DifficultiesNanoparticle-food matrix interaction, nanoparticle tracing in the gut and in the bodyMatrix InteractionsLargely unknown

UncertaintiesGI fate, nanoparticle degradation, uptake through the gut, biodistribution, metabolism, excretion, toxicity



Sub-Group 2: Material CharacteristicsEmulsions, Dispersions & Powders Thereof

Definition and UsagePreparations of water-immiscible nutrients and additives, designed for stabilisation, ease of handling, delivery or organoleptic properties. Various preparation methods for emulsions and dispersions in water are available, powder production involves the use of soluble biopolymer and spray-drying or other similar method.

Requirements for Characterisation• Digestibility• Particle size distribution• Composition & Charge

UncertaintiesWhether there is direct absorption from the GI tract, thus circumventing normal physiological digestion.

Analytical Gaps and Difficulties• Sample preparation: what to model (as produced, as used, as prepared, GI environment)• Representative number-size distribution, lack of analytical methods suitable for emulsions

Matrix InteractionsExacerbation of the above due to interference from complex matricies‘Black box’ …..



Requirement Key Points Difficulty

Composition - -

Surface physico-chemistry In what environment Multiple-steps

Morphological aspects Where in the food-chain to characterise

Multiple-steps

Size (incl agglo/aggre) Appropriate unit Method to suit appropriate unit

‘Sample prep’ Preparation causes change

Shape May not be homogeneous quantification

Digestability Qualification & quantification of direct uptake?

All of the above

Summary



Conclusion

o As far as can be ascertained current ‘nano-sized’ ingredients are minerals, silver and new nutrient/additive preparations.

o Silver, ceramics and clays are used in contact materials.o List of required measurands is limited.o However, almost all measurands present difficulty:

what product stage should be considered?• matrix effects are mostly unknown.

what method(s) is suitable for sample preparation and analysis?



Conclusion

As formulated

As manufactured

As prepared

As eaten

As passaged in GI

Ease of Analysis

Matrix Complexity

Matrix Diversity



Documents

NanoRelease Task Group 1: Material Characteristics Characteristics Relevant to Uptake and Bioavailability 1