K a s h a n U n i v e r s i t yD e p a r t m e n t o f C h e m i s t r y

G r o u p o f O r g a n i c C h e m i s t r y

Master Degree Seminar Subject:

Organic Nano Particles

(ONPs)Synthesis, Properties and

applicationsSuperviser: Dr Leila MoradiBy: Mahdi Mirzaie

November. 2015

Contents

◎Introduction◎Prepartion and Synthesis◎Properties◎Applications◎Conclusion

Introduction: Type of ONPs

◎Carbon nanomaterials◎Other organic materials

◎fluorescent organic nanoparticles (FONs)◎water soluble organic nano particles◎Starch nanoparticles :SNPs◎Metal Organic Frameworks (MOPs)

◎Nanochemistry: pass form the Microscale level to nanosize

◎Discovery of size effect

Reason for delaying studies the ONps vs Metal Nanopartiles :

-Low Melting Tempratures

- Lesser thermal Stability

- Then: limit the methods for their synthesis and applications

- Believed that no size effect is manifested in ONPs (Wrong)

Prepartion and Synthesis

Factors for Select the methoods

◎Particle Size◎Size Distribution◎Stability of Synthesized Systems◎Solubility

Methods for the fabrication of nanoparticles

◎bottom-up: Chemical Methods

◎top-down: Physical Methods

Physical Methods

◎Mechanical Grinding

◎Laser Ablation

Grinding

Dry

Ball mills Jet Mills

Wet

Dissocubes

◎Ball Mill ◎Jet Mill

Grinding of ibuprofen by the jet milling technology

◎particles measuring from 1 to 7 nm, SEM image

◎Source: Rasenack, N.; Steckel, H.; Muller, B. W. Powder Technol. 2004, 143, 291.

stabilization

◎For unstable particles : stabilization was achieved by adding cellulose ethers or poly(vinylpyrrolidone), The particles acquired a positive charge that kept them from agglomeration

◎Source: Liversidge, E.M.; Liversidge, G.G. Adv. Drug Del. Rev. 2011, 63, 427◎Source: US P. 5628981 (1997)

drawbacks of the mechanical synthesis

• Impurities from the mill

•destruction of thermally unstable

•the presence of a relatively large number of particles

•limited possibility of a control over the size and thetheir wide size distribution, and also their irregular shape

Laser Ablation

◎Application in ONPs back to 2000

◎Prepartion of suspensin◎ impact of an intense laser pulse

fragmentation of grains , transparent colloidal solution

Source: Sugiyama, T.; Asahi, T.; Yuyama, K.; Takeuchi, H.; Jeon, H.; Hosokawa, Y.; Masuhara, H. Proc. SPIE 2008, 6891, 37.

◎preparation of stable colloidal solutions in the absence of stabilizers.◎control the size : wavelength, the laser pulse width, and fluence

◎increase in the laser-radiation fluence results in a decrease in the nanoparticle size

◎nanosecond region: photothermal

◎femtosecond region: photomechanical

◎Source: Sergeev, G.B. In Nanokhimiya: Uchebnoe Posobie Nanochemistry: The Manual, Moscow:Izd. KDU, 2006, p 336.

Example

◎20 nm particles of indometacin , a drug used for treating epilepsy

◎pulse width of 8 ns: size was 40–60 nm ◎and did not depend on the nature of substance.

◎With pulse width of 150 fs : smaller particles could be synthesized.

◎Source: Nagare, S.; Senna, M. Solid State Ionics 2004, 172, 243.

SEM image of quinacridone particles obtained upon laser radiation of wavelength 355 nm, pulse duration 8 ns, and fluence 100 mJ cm

Drawbacks of the laser ablation method

◎only a small amount of dispersion is formed

◎may cause photochemical decomposition

Chemical Methods

•Solvent Replacement

•Antisolvents for Precipitation

•Chemical Reduction in Solution

•Ion Association

•Synthesis of Nanoparticles in Water–Oil Emulsion

•Photochemical Method

•The use of Supercritical Fluids

•Cryochemical Synthesis and Modification of Nanoparticles

Solvent Replacement

◎ Carotene and PVP were dissolved in chloroform, and then chloroform was evaporated in vacuo to form a solid mixture of β-carotene and PVP. Upon the addition of water to the solid mixture, an aqueous colloidal solution formed, which was called “ hydrosol”

◎Source: Li, S.; He, L.; Xiong, F.; Li, Y.; Yang, G. J. Phys. Chem. B 2004, 108, 10887.

Example

◎perylene particles with an average size of 100 nm were obtained by pouring the 0.25 × 10-3 M perylene solution in acetone to water with vigorous stirring

◎Source: Mori, J.; Miyashita, Y.; Oliveira, D.; Kasai, H.; Oikawa, H.; Nakanishi, H. J. Cryst. Growth, 2009, 311, 553

Benefits

◎mild conditions

◎for thermally unstable compounds

◎relatively simple and accessible

◎Drawbacks

◎Low production performance

◎cannot be used for substances poorly soluble in organic solvents

◎Very dilute solutions are obtained

Synthesis of Nanoparticles in Water–Oil Emulsion

◎(1) preparation of the oil-in-water emulsion by stirring;◎ (2) transfer of nanoparticles into the water phase, for example, by sonication or high-pressure homogenization

◎Source: Margulis-Goshen, K.; Netivi, H. D.; Major, D. T.; Gradzielski, M.; Raviv, U.; Magdass, S. J. Colloid Interface Sci. 2010, 342, 283.

Example

◎by sonication : nanoparticles of tetracene measuring 85 nm and anthracene measuring 75 nm were prepared

◎From microemulsions containing sodium dodecyl sulfate as the surfactant, nanoparticles of propylparaben with the sizes of 40–70 nm were obtained.

Cryochemical

◎Cryochemistry studies the reactions proceeding at low (77 K) and ultralow (4 K) temperatures.

◎The cryodrying includes the following stages: • deep Freezing• primary drying• secondary drying (freeze-drying (cryodrying) or cryoextraction)

Properties

Detection and characterization

Sample Preparation (Filteration, Centrifugation)

Imaging (TEM, SEM, AFM)

Separation (HPLC)

Characterization

NMR Applications in ONPs

◎Phase transitions of the nanoparticle matrix

◎Molecular exchange on the nanoparticle surface

◎Molecular exchange through nanocapsule walls

◎Local phase separations

◎Particle degradation

◎Assignment to structural elements of particle dispersions

NMR

Benfits

Study of nanoparticles dispersions

In Drugs:-Release properties-Surface exchange process-Decomposition pathways

Disadvantages

Poor SensitivityTime consuming

Source: Trends in Analytical Chemistry, Vol. 30, No. 1, 2011

Notes

◎The dependence of the Stokes shift in the molecular spectra on the size of organic particles was revealed

◎The restriction for the exchange interactions in organic nanoparticles brings about an increase in the nonlinear optical characteristics

◎ It was shown that with the increase in the particle size, the luminescence decreased

◎Increase in particle size, decrease in luminescense

Applications

Applications

◎Drug: poorly water-soluble drug◎Food ◎Gene therapy◎Sensors◎Catalyst

Flourscent organic nanoparticles

◎Organic Light Emitting Diodes (OLED)◎The photoluminescence of solid nanoparticles was 700 times (!) more intense than that of its solution

Multicolor emision

◎1,2,3,4,5-pentaphenylcyclopenta-1,3-diene

◎ Source: Zhao, Y. S.; Fu, H.; Hu, F.; Peng, A.; Yao, J. Adv. Mater. 2007, 19, 3554.

Food

Based of degradable polymers (lipid proteins, polysaccharides)

-Basic food materialsNano cluster: Starch based biopolymers: Modifier

-Food processingOil fresh 1000: Nanosized modified surface: Catalyst

- Food product/SupplemnetsLypo-spheric Vitamin C: Liposomal nanospheres: Carrier

Source: Trends in Analytical Chemistry, Vol. 30, No. 1, 2011

Source:http://dx.doi.org/doi:10.1016/j.snb.2014.09.031

Drugs

◎poorly water-soluble drug : Solubility of drugs is one of the properties that determine their efficacy◎The calculated and measured solubility values sometimes differed from 2–3-fold to 20-fold

◎The drug celecoxib , poorly soluble in waterProduction of amorphous nanoparticles of this drug measuring 17 nm increased its dissolution rate by 10-fold

Conclusion

◎The Problem of stabilizing organic nanoparticles

◎enhancing the efficiency of the methods of their fabrication

◎reducing their cost

◎Now: grinding is only method for manufacturing ONPs

Thanks!Any questions?

You can find me at:mirzaie@alum.sharif.edu

Download : www.slideshare.com/mirzaie1986