Organic dye nanoparticles

Yao H (2010) Prospects for organic dye nanoparticles. In Demchenko AP (ed) Advanced fluorescence reporters in chemistry and biology. II. Springer Ser Fluoresc 9 285-303... 

Keywords Aggregation-induced enhanced emission (AIEE) Fluorescent organic nanoparticles Ion-association method Organic dye nanoparticles Reprecipitation method Restriction of intramolecular rotation Size-dependent optical properties... 

Introduction Organic Dye Nanoparticles Exhibit Unique Physicochemical Properties... 

Fabrication of organic dye nanoparticles and the ability to tailor their photophysical characteristics represent an important challenge, although they have been paid little attention principally due to the following two factors (1) Owing to their... 

It is of fundamental and technological interest to understand how physicochemical properties of organic dye nanoparticles develop as a function of size. The first step to reach this goal is to synthesize well-defined organic dye nanoparticles in a controlled manner. 

The present author has developed a novel method called ion-association method. This is also a simple and versatile method for the preparation of ion-based organic dye nanoparticles in pure aqueous solution by the ion association approach [23]. It utilizes the control of hydrophilicity/hydrophobicity of the ionic material itself via ion-pair formation for example, addition of a cationic target dye solution into aqueous solution containing a certain kind of hydrophobic anions forms an electrically neutral ion-pair because of the strong electrostatic attraction, followed by aggregation of ion-pair species originated from van der Waals attractive interactions between them to produce nuclei and the subsequent nanoparticles (Fig. 3). In this case, hydrophobic but water-soluble anions, such as tetraphenyl-borate (TPB) or its derivatives (tetrakis(4-fluorophenyl)borate (TFPB), tetrakis [3,5-... 

Fig. 3 Concept of the ion-association method for fabricating ion-based organic dye nanoparticles in pure aqueous media. The approach is based on ion-pair formation between the ionic dye (for example, cationic dye) and the hydrophobic counterion that is soluble in water [for example, tetraphenylborate (TPB) or its derivative anion], which gives rise to a hydrophobic phase in water. For preparation, organic cosolvent is unnecessary. The size of the dye nanoparticles can be controlled by adjusting the interionic interaction between the dye cation and the associative hydrophobic counteranion...

Anion-based organic dye nanoparticles can be also synthesized on the basis of the ion-association method. In this case, hydrophobic phosphazenium cations such as tetrakis[tris(dimethylamino) phosphoranylideneamino]phosphonium cation are effective for ion-pair formation with anionic dyes. A neutral polymer stabilizer polyvinylpyrrolidone (PVP) that is soluble in water is sometimes added for preventing agglomeration... 

Fig. 5 A proposed mechanism for enhanced emission (or AIEE) in solid-state organic dye nanoparticles. The dye considered here is trans-biphenylethylene (CN-MBE) compound. The geometry is optimized by the density functional theory (DFT) calculation at the B3LYP/6-31G level. Molecular distortion such as twisting and/or subsequent planarization causes prevention of radiationless processes along with specific aggregation such as the /-aggregate in the nanoparticles...

Organic dye nanoparticles of DHIA and DHBIA (the chemical structures are shown in Fig. 1) have been synthesized in THF/water mixed solvent by a reprecipitation method [32]. These dye molecules possess a 2-(2-hydroxyphenyl) benzothiazole (HBT) unit, which is known to be more stable as an enol imine form in the ground state and as a keto amine form in the excited state [32, 33] (Fig. 6). The nanoparticles exhibited the AIEE phenomenon mainly due to a restricted intramolecular motion, that is, impediment to free rotation of two end-substituted HBT units around single bonds. It is interesting to note that the... 

---