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Guodong Sui, Miodrag Micic, Qun Huo and Roger M. Leblanc- Studies of a novel polymerizable amphiphilic dendrimer

Guodong Sui, Miodrag Micic, Qun Huo and Roger M. Leblanc- Studies of a novel polymerizable amphiphilic dendrimer

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Colloids and Surfaces A: Physicochemical and Engineering Aspects 171 (2000) 185 – 197 www.elsevier.

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Studies of a novel polymerizable amphiphilic dendrimer
Guodong Sui, Miodrag Micic, Qun Huo, Roger M. Leblanc *
Department of Chemistry, Center for Supramolecular Science, Cox Science Building-Room 315, Uni6ersity of Miami, PO Box 249118, Coral Gables, FL 33124, USA

Abstract In the present study, we have synthesized a polymerizable amphiphilic dendrimer by attaching 10,12-pentacosadiynoic acid (PDA) to a third generation poly(amidoamine) (PAMAM) dendrimer core (PDA-PAMAM). This dendrimer was characterized by 1H NMR and MALDI-TOF mass spectroscopy. The amphiphilic property of this dendrimer has been studied. Surface pressure and surface dipole moment – area isotherm measurements have shown , that PDA-PAMAM forms a stable monolayer at the air – water interface with a limiting molecular area of 460 A2 per molecule. The compressed monolayer can be readily polymerized upon UV irradiation, as like other PDA derivatives. The topography of the monolayer was observed by Brewster angle microscopy (BAM) as well as by the environmental scanning electron microscopy (ESEM). We found a good correlation between the size and shape of monolayer domains observed with the BAM and ESEM techniques. To our knowledge, this is the first time wet mode ESEM has been used to characterize L–B film. The wet mode ensures that L – B films remain intact without being damaged by the high vacuum system of traditional SEM. As a preliminary study, we have found that this new dendrimer forms colloidal particles in chloroform solution and can be readily polymerized by UV irradiation. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Dendrimer; ESEM; PAMAM; PDA; PDA-PAMAM

1. Introduction Dendrimers represent a new class of synthetic macromolecules characterized by a regularly branched treelike structure [1]. Recently the dendritic structures have attracted increasing attention for their potential applications in molecular recognition [2], building blocks for self assembly process [3], catalysis [4], encapsulation and con* Corresponding author. Tel.: +1-305-2842282; fax: +1305-2844571. E-mail address: rml@umiami.ir.miami.edu (R.M. Leblanc)

trolled release [5], chemical sensors [6], biomimetic materials [7,8], metal nanoclusters [9] and so on. The end functional groups of dendrimers are confined in space and are present at the periphery of the molecule. Therefore, dendrimers become unique starting materials for numerous chemical modifications. End group modification is particularly attractive for dendrimers made by the divergent approach. From this class of compounds, the poly(amidoamine) dendrimer (PAMAM dendrimer) [10,11], the arborols [12], and the poly(propylene imine) dendrimers (DAB-dendr(NH2)x ) [13] are among those most frequently

0927-7757/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 5 5 3 - 1

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studied on account of their availability on a reasonable large scale, even for the higher-generation dendrimers. Recently it has been reported on the preparation of dendritic inverted unimolecular micelles as a new class of macromolecular structures by attaching polar end groups to the PAMAM or DAB-dendr-(NH2)x dentritic cores. Barrs et al. [14–17] have synthesized a series of amphiphilic dendrimers by PAMAM dendrimer and the DABdendr-(NH2)x with a variety of hydrophobic alkyl chains. These compounds were able to encapsulate guest molecules and could be used as very effective extractants in liquid – liquid extractions. As a result of their amphiphilic nature, these types of dendrimers are suitable building blocks for the construction of supramolecular architectures in both solution and air – water interface. They also represent a novel class of surfactants. Langmuir film studies at the air – water interface demonstrated that these molecules are able to arrange themselves in monolayers in which the dendrimer part of the molecule is in contact with the water subphase and all the alkyl chains point to the air. Although the ambivalent nature of dendrimers make it possible to form monolayers on surface of solid substrate or aqueous solution, work in this field is not extensively investigated yet. Much of the fundamental knowledge and application aspects of amphiphilic dendrimer remain unclear. Beyond the PAMAM and DAB-dendr-(NH2)x monolayers, carbosilane dendrimer [18], polystyrene dendrimer [19] and polyether dendrimer [20] Langmuir or L – B films have also been studied by techniques such as the surface pressure and surface dipole moment – area isotherm measurements, Brewster angle microscope and scanning force microscope methods. Polydiacetylenes represent an important class of polymers, which have attracted continuous attention due to their unique electronic and optical properties. Diacetylenes substituted with various side chains readily undergo photopolymerization to form an ene-yne alternated polymer chain upon UV irradiation (254 nm) in a wide range of organized structures, such as single crystals, Langmuir–Blodgett films, self-assembled monolayers, liposomes or vesicles, and solutions [21]. The re-

sulting one-dimensional conjugated polydiacetylene backbone shows large nonlinear optical susceptibilities comparable to inorganic semiconductors with ultrafast response time. The chromatic property of polydiacetylenes is of particular interest in the recent years. The highly sensitive chromatic exchange of polydiacetylene between blue and red forms can be potentially used in the development of optical biosensors [21]. In the present study, we report the synthesis and study of an amphiphilic dendrimer with polymerizable diacetylene alkyl chains attached to the dendrimer core. The free amino groups on the third generation PAMAM dendrimer are capped with sixteen 10,12-pentacosadiynoic acid chains (Fig. 1). We have two main purposes behind this study. Firstly, we would like to reveal more about the fundamental aspects of a monolayer property of this macromolecular dendrimer at the air–water interface by using different thermodynamic, spectroscopic and microscopic techniques. Secondly, it will be interesting to examine the photopolymerization behavior of this macromolecule both in solution and at the air–water interface. The polymerization may lead to the design of novel macromolecules with unique electronic and optical properties as exhibited in other polydiacetylene compounds.

2. Experimental section

2.1. Materials
Starburst PAMAM (generation 3) dendrimer and other chemicals were purchased from Aldrich Chemical (Milwaukee, WI), and were used in organic synthesis directly. All organic solvents for the synthesis were purchased from Fisher Scientific (Norcross, GA), as reagent grade and were used without further purification. 10,12-Pentacosadiynoic acid was purchased from GSF Chemical (Powell, OH) and recrystallized from petroleum ether before use. The 1H NMR spectra were recorded on a Varian VXR 400 MHz spectrometer. The IR spectrum was obtained from a Perkin–Elmer PE-GRAMS/2000 FT-IR spectrometer. UV-VIS spectra were performed from

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HP8452A Hewlett– Packard 8452A diode array spectrophotometer. University of Illinois, School of Chemical Sciences, conducted the MALDITOF mass spectrum.

2.2. Synthesis
To the 7 ml dichloromethane solution of the PDA succinimidyl ester (150 mg, MW 471 g mol − 1, 0.3 mmol), 300 ml starburst PAMAM dendrimer (generation 3, 20 wt% in methyl alcohol, 0.015 mmol) was added within 20 min and the solution was stirred vigorously for 24 h. The solution was concentrated en vacuo. To the left

white solids, 50 ml 1 N NaOH solution was added and the suspension was maintained at 60°C for 6 h. The suspension was filtered, and the solids were washed with 1 N NaOH solution, followed by distilled water and demineralized water. After vacuum dried, the product was obtained as white solids with a yield of 110 mg, 65.6%. 1H NMR (CDCl3): l 0.85 (t, 48H); 1.23 (m, 578H); 1.50 (m, 170H); 2.2 (m, 88H); 3.3 (m, 44H). IR (cm − 1, CHCl3 as solvent): 3490 s; 2900 s; 2100 w; 1650 s; 800 s. MALDI-TOF MS calculated for C452H928O44N58, m/z 8948.0, found 8981.7 (compound was dissolved in CHCl3/CF3COOH mixture solvent (v:v, 80:1)).

Fig. 1. Structure of new dendrimer PDA-PAMAM.

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2.3. General methods for surface chemistry studies
All the surface chemistry studies were conducted in a clean room class 1000 where temperature (2091°C) and humidity (509 1%) were controlled. The chloroform used in monolayer studies was purchased from Fisher Scientific, as HPLC grade. The water used for the monolayer study was purified by a Modulab 2020 water purification system (Continental Water System, San Antonio, TX) with a specific resistivity of 18 MV · cm and a surface tension of 72.6 mN m − 1 at 20 9 1°C. The injection volume of the dendrimer solution (0.1 mg ml − 1, CHCl3/CF3COOH mixture solvent (v:v, 80:1)) was 30 ml for the surface pressure measurements, 70 ml for the surface potential measurements and 40 ml for the Brewster angle experiments. After the sample was spread, a 15 min period was allowed to pass by for the complete evaporation of solvent before compres, sion. The compression rate was set up at 5 A2 molecule − 1 min − 1 for all the experiments. Three different Langmuir troughs were used. The Langmuir trough used for the surface pressure measurements was a KSV minitrough (KSV Instrument, Helsinki, Finland). Two computer controlled symmetrically movable barriers were used to regulate the surface area. The trough dimensions are 7.5×30 cm. The surface pressure was measured by the Wilhelmy method. The sensitivity of the Wilhelmy plate is 90.01 mN m − 1. The isotherm presented is an average of three measurements. An UV-Vis spectrophotometer (Hewlett –Packard, Wilmington, DE) can be slid over the KSV trough for recording the absorption spectra of the dendrimer monolayer directly at the air–water interface. The UV lamp of the spectrophotometer is also the light source for the irradiation. The power of the light on the monolayer at 254 nm is 0.6 W m − 2. The Langmuir trough used for the surface potential measurements is a home-made trough. Two symmetrically movable barriers controlled by the computer were used to regulate the surface area. The dimensions of this trough are 0.6× 12 ×100 cm. The surface potential was measured using the ionizing electrode method. A reference platinum electrode was immersed in the reference trough compartment

and an americium electrode (Am241) was placed about 1–2 mm above the monolayer under study. For the Brewster angle microscopy studies, a Nippon trough (5× 47 cm) equipped with a moving wall system (NL-LB 140SMWC, Nippon Laser and Electronics Lab., Nagoya, Japan), a helium-neon laser (wavelength 632.8 nm and power 10 mW), and a CCD camera. The images from the CCD was captured and digitized using a digital video capture mode (Snappy video Snapshot, Rancho Cordova, CA) for further analysis. The 3-D representations of the BAM images were also presented using a software NIH 1.62 image that allow noise reduction using a low pass filter. The dark areas of the image represent the valleys whereas the bright areas represent high peaks in the 3-D figures. All the images presented in this work have dimensions of 400×400 mm. For the ESEM studies, we used a Philips/Electroscan environmental scanning electron microscope, XL 30, with a field emission electron gun. Horizontal lift method was used to deposit PDAPAMAM monolayer to the surface of the highly oriented pyrolytic graphite (HOPG) which was purchased from Adv. Ceramic, OH. Two different L–B films were prepared, one at a surface pressure of 15 and the other of 35 mN m − 1. All the images were obtained at an ambient temperature of 20°C. In order to get the optimal picture quality in terms of resolution and contrast ratio, we varied humidity and pressure (water vapor atmosphere with pressure varying from 4 to 6 Torr) inside the chamber.

3. Results and discussions

3.1. Surface pressure and surface dipole moment–area isotherms
The surface pressure–area isotherm (Fig. 2) shows that the PDA-PAMAM dendrimer forms a monolayer at the air–water interface which evolves from a liquid expanded phase between surface pressure 0 and 8 mN m − 1 to a liquid condensed phase at surface pressure between 8 and 40 mN m − 1. The limiting molecular area was obtained by the extrapolation of the liquid con-

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Fig. 2. Surface pressure (y)–area (A) and surface dipole moment (vÞ) –area (A) isotherms of the PDA-PAMAM dendrimer monolayer at air–water interface.

Fig. 3. Structure of the PDA-PAMAM dendrimer molecular model.

densed part of the isotherm at surface pressure nil , with a value of 460 A2 molecule − 1. This result agrees with the previous measurements on a palmitoyl alkyl chain modified third generation

DAB-dendr-(NH2)16 dendrimer [13], of which the , obtained limiting molecular area is about 480 A2 molecule − 1. From the modeling of the PDA-PAMAM dendrimer (Hyperchem Software), the whole molecule adopts a flat shape with the hydrophobic alkyl chains fully extended toward the outside of the dendrimer core (Fig. 3). The molecular area of PDA-PAMAM in this conformation is about , 8200 A2 molecule − 1 and the molecular area of the hydrophilic core (the PAMAM dendrimer part) is , 1880 A2 molecule − 1. None of these numbers corresponds to the limiting molecular area. In the other hands, the limiting molecular area of one , PDA alkyl chain is : 25–30 A2 molecule − 1, and the total molecular area of sixteen PDA alkyl , chains would be around 480 A2 molecule − 1. The limiting molecular area we obtained is approximately equivalent to the total molecular area of 16 alkyl chains. This result indicates that when the PDA-PAMAM dendrimer monolayer is compressed to a liquid condensed phase, the whole molecule is highly compact. Not only all the hydrophobic chains stand up, but also the hydrophilic core is distorted and compacts. The surface potential technique measures the dipole moment changes of the monolayer [22]. Surface potential values are frequently expressed alternately in terms of surface dipole moments, vÞ calculated, from the equation, vÞ = A · DV/12y [23]. The surface dipole moment is a more realistic indicator of the monolayer reorientation process. We have obtained the vÞ –A curve (Fig. 2) of the PDA-PAMAM dendrimer monolayer from the surface potential–area isotherm. The dipole moment of the monolayer is directly related to the packing density and molecular orientation within the film. Before compression, the amphiphile molecules exist randomly in a gas phase at the air–water interface. The total dipole moment contribution from the amphiphile molecules is zero, due to the random distribution of the amphiphile molecules. With the compression, the surface dipole moment of the monolayer starts to increase and the amphiphiles start to orient themselves to form an organized monolayer. When the monolayer reaches a liquid condensed phase, the sur-

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face dipole moment reaches its maximum value. The difference between this maximum value and the surface dipole moment at clean water represents the total surface dipole moment contribution from the monolayer molecules. From the surface dipole moment – area isotherm of PDAPAMAM, one can see that the surface dipole moment starts to increase at molecular area of , 1700 A2 molecule − 1. That means that all the molecular dipoles of the dendrimer are being oriented vertically and the dendrimer molecules begin to organize themselves on the surface by orienting their hydrophobic chains directed into air. After increasing at a relatively low speed from , molecular area of 1400 – 900 A2 molecule − 1, the surface dipole moment increases steadily, which indicates that all the hydrophobic chains have been orientated vertically into air. The surface dipole moment reaches its highest value at molec, ular area of 400 A2 molecule − 1. This result corresponds to what has been observed from the surface pressure –area isotherm. At molecular , area of 400 A2 molecule − 1, the monolayer is in a liquid condensed phase and all the molecules are tightly packed. The total surface dipole moment contribution from the monolayer reaches its highest value and the surface dipole moment remains unchanged with continuous compression. There are several structure models [24 – 27] such as the ‘edge-on’ and ‘face-on’ models [24,25] which were quite useful in analyzing the monolayer structures. By comparing with the molecular dimensions of the CPK model of PDA-PAMAM molecule, we have proposed a model to describe the orientational and conformational change of PDA-PAMAM monolayer during the compression, as shown in the cartoon picture of Fig. 2. A noteworthy point that needs to be addressed here is the surface dipole moment increase of the PDA-PAMAM monolayer at molecular area of , 1700 A2 molecule − 1. Before compression, the dendrimers are lying flat at the air – water interface. When compressed to molecular area about , 1700 A2 molecule − 1, which is approximately equivalent to the size of the dendrimer core, the hydrophobic long tail starts to lift up and the surface dipole moment of the monolayer starts to increase. After all the alkyl chains are oriented

towards the air, the surface dipole moment increases very slowly for a certain time until the area is further decreased. At this stage, the hydrophilic core of the molecule also starts to be compressed and the surface dipole moment increases again until a highly compact monolayer is formed. At this final stage, the hydrophilic dendrimer core must be highly distorted to a non-planar structure as illustrated in Fig. 2. This also indicates that dendrimer core is a very flexible structure at the air–water interface.

3.2. Brewster angle microscopy and en6ironmental scanning electron microscopy
In the recent years, the Brewster angle microscopy is frequently used in the characterization of monolayers at the air–water interface [28–30]. The topography of the PDA-PAMAM monolayer at the air–water interface has been observed through Brewster angle microscope. Previous study [15] has pointed out the formation of preaggregates of amphiphilic dendrimers on the water surface before compression due to the strong van der Waals interactions between the hydrophobic alkyl chains. This was also observed in the present study, as indicated in the BAM images of the monolayer at nil surface pressure (Fig. 4A). Particularly, large patches of monolayer (bright areas) are seen with some small holes (dark areas) randomly distributed in the patches. The holes have an average diameter of 10–20 mm. With continuous compression, the topography of the monolayer becomes more and more homogeneous, as shown in the BAM images obtained at surface pressure of 15 and 35 mN m − 1 (Fig. 4B,C). The dark holes become less and less obvious. We attribute the appearance of the dark holes to the self-assembling pattern of the PDAPAMAM molecules at the air–water interface such as illustrated in Fig. 5. The hydrophobic van der Waals interactions must be the driving force behind this self-assembling. As an interesting preliminary investigation, we have used the environmental scanning electron microscope (ESEM) to observe the topography of one layer PDA-PAMAM Langmuir–Blodgett film. ESEM represents a variation of the scanning

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Fig. 4. Brewster angle microscope images of PDA-PAMAM dendrimer monolayer observed at different surface pressures: (A) 0 mN m − 1; (B) 15 mN m − 1; (C) 35 mN m − 1.

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electron microscope [31] in which high vacuum chamber is separated from the sample compartment by a system of small apertures, allowing sample to be examined under controlled atmosphere instead of high vacuum conditions. Moreover, non-conducting samples do not need conductive coating in order to be observed. These technical advantages make ESEM ideal for the investigations of thin organic films. Traditional SEM has been used to observe the topography of the Langmuir –Blodgett films. However, traditional SEM requires high vacuum ( : 10 − 8 Torr) to operate and under such a high vacuum, the films are very easily damaged and the observed image may not reflect the real topography of the films. As a new detection configuration for conventional SEM, ESEM retains the main advantages of SEM while allowing the imaging of a sample in its natural state by maintaining a minimum water vapor pressure in the specimen chamber. Since ESEM is operated in a relatively low vacuum, the risk of losing or damaging the film by the high vacuum system is greatly reduced. In this study, we have successfully used the ESEM to observe the topography of one layer PDA-PAMAM L– B film with water vapor pressure of 4–6 Torr, as presented in Fig. 6. First, we have found good correlation between size and shape of monolayer domains observed with BAM

and ESEM techniques. In the ESEM images (Fig. 6A–C), the topography of the monolayer obtained at surface pressure of 15 mN m − 1 exhibits similar domains as well as black holes as observed from the BAM images. With increased surface pressure, ESEM images also indicate that the topography of monolayer becomes more homogeneous and compact (Fig. 6D–F vs. Fig. 6A–C). More importantly, we have found that ESEM can have a better resolution to study the domain structures of monolayer. As shown in Fig. 6C, we can clearly see hundreds of nm scale structures of the monolayer domains. At surface pressure of 35 mN m − 1, even though the monolayer seems quite homogeneous as observed in the 100s mm scale, we can still see small black holes with 100 nm scales existing in the monolayer patches when we observe the surface topography at magnification× 20 000 times. BAM technique obviously lacks such a high resolution. Our study suggests that ESEM can become a very reliable, convenient and precise microscopic technique to study the topography of Langmuir–Blodgett films in the near future.

3.3. Photopolymerization of the PDA-PAMAM monolayer
As one of our purpose to design PDA-PAMAM, we would like to study the photopolymerization of PDA-PAMAM monolayer at the air–water interface. As presented in Fig. 7, the PDA-PAMAM monolayer can be readily polymerized upon UV irradiation. The polymerized monolayer exhibits a typical blue form absorption band at 630 nm as well as absorption at 570 nm and the polymerization reaches a maximum extent very quickly. From the previous discussion, we know that at surface pressure of 35 mN m − 1, the hydrophobic chains of the PDA-PAMAM are lifted towards the air and are highly compact in the monolayer. With such close packing, the topochemical photopolymerization between the diacetylene groups can readily take place. As a matter of fact, we can easily see the polymerized blue film on the water surface with the naked eye. A noteworthy point is the chromatic property of PDA-PAMAM monolayer upon prolonged UV

Fig. 5. An illustration to explain the black holes in the PDA-PAMAM monolayer domains.

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Fig. 6. ESEM images of one layer PDA-PAMAM dendrimer L – B film obtained at different surface pressures: A – C: 15 mN m − 1; D –F: 35 mN m − 1. The image magnifications (bar) are the following: (A), 10 mm; (B), 1 mm; (C), 500 nm; (D), 20 mm; (E), 10 mm; (F), 1 mm.

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Fig. 6. (Continued)

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Fig. 7. UV-Vis absorption spectra of polymerized PDA-PAMAM dendrimer monolayer (surface pressure 15 mN m − 1) during different photo-irradiation times.

irradiation. In contrast to most of the previously studied polydiacetylenes [21], there is no obvious red form absorption band appearing with increased irradiation time on the PDA-PAMAM monolayer. Since all the alkyl chains from the dendrimer molecules are closely packed, the propagation of the polymer backbone extends from one dendrimer to another dendrimer, leading to the formation of highly branched polymerized macromolecules at air – water interface.

3.4. Photopolymerization of PDA-PAMAM in solution
It has been previously reported that amphiphilic dendrimers aggregate to form nanoscale particles in aqueous solution [26]. The van der Waals interactions between the large number of hydrophobic alkyl chains should be the driving force behind the formation of these aggregates. While hydrogen bonding has been used extensively as a non covalent tool in the design of supramolecular self-assemblies, the hydrophobic van der Waals interactions have not receive enough attention in similar studies. A few groups have recently noticed that the hydrophobic molecular interactions may become a dominant factor like hydrogen bonding in the formation of supramolecular self-assemblies in solution [32].

Since the PDA-PAMAM dendrimer contains sixteen hydrophobic alkyl chains surrounding the hydrophilic dendrimer core, we feel it will be very interesting to see whether this dendrimer can form a supramolecular self-assembly in solution as illustrated in Fig. 8. As shown from the modeling structure of this molecule, the distance between the diacetylene groups on different alkyl chains is , at least about 7 A away from each other. That means it is impossible for the diacetylene groups from the same dendrimer molecule to polymerize together in solution, since the topochemical photopolymerization requires a distance between di, acetylene groups within 4–5 A. However, if the dendrimer molecules self-assemble to form a supramolecule as illustrated in Fig. 8, we should be able to polymerize the supramolecule along the self-assembling direction and at the end, the supramolecular assembly will become a unimacromolecule with a long fiber-like structure. The sixteen polydiacetylene backbones thus created in the same macromolecule may lead to some potential applications based on the unique properties of polydiacetylenes. We have found that in chloroform at a concentration of 10 − 5 M, the PDA-PAMAM forms an opalescent solution and the dispersion can remain unprecipitated for one month when kept in dark. It is certain that the PDA-PAMAM forms colloidal particles in chloroform solution as found in

Fig. 8. A plausible supramolecular structure of the PDA-PAMAM dendrimer colloidal particles in CHCl3 solution.

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Fig. 9. UV-Vis absorption spectra of the PDA-PAMAM dendrimer during different photo-irradiation times in CHCl3 solution (10 − 3 M).

other amphiphilic dendrimers [26]. We have tried to irradiate this opalescent solution in a UV quarts cell and the absorption spectra with different irradiation time are presented (Fig. 9). The PDA-PAMAM particles can be easily polymerized within a time period of a few s to give a blue form absorption band at 640 nm and a side band at 590 nm. The opalescent solution became deep blue almost immediately upon exposure to UV light. With prolonged irradiation, the absorption at 590 nm became stronger and stronger and at last a strong absorption at 530 nm as well as absorption at 490 nm appeared. And the solution became deep purple, as indicated in the appearance of a red form absorption band in the UV spectra after irradiation of 500 s. Since we know it is very unlikely that the diacetylene groups from the same dendrimer polymerize together, the observed polymerization must extend from one dendrimer to another dendrimer. We are currently working on the more detailed characterization of the nature of PDA-PAMAM particles before and after polymerization. We expect these studies might provide a new approach in the design of special macromolecules with well-defined three dimensional structures along the direction of single molecule“supramolecular self-assembly“ macromolecule.

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