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Self-assembly techniques are powerful and efficient methods for the synthesis of nanoscale materials. Using these techniques and their combination with other bottom-up fabrication processes, materials with hierarchical features can be produced with form and function in multiple length scales. We synthesize multifunctional nanoparticles through surfactant-assisted noncovalent interactions using nanoparticle building blocks. Self-assembly of these nano-building blocks results in functional materials that exhibit well-defined morphologies and hierarchical architectures for a wide range of applications. Hierarchically structured porphyrin nanocrystals can be synthesized through surfactant micelle-confined noncovalent interactions of photoactive porphyrins. We can amplify the intrinsic advantages of individual photoactive porphyrins by engineering them into well-defined active nanostructures. Through kinetic control, these nanocrystals exhibit precisely defined size, shape, and spatial arrangement of the individual porphyrins, which facilitates intermolecular mass and energy transfer. These self-assembly techniques provide remarkable flexibility to design morphologies and architectures that produce desirable properties for practical applications including photocatalysis, photodegradation, and phototherapy.
Achieving control over the morphology of conjugated polymer (CP) blends at nanoscale is crucial for enhancing their performances in diverse organic optoelectronic devices, including thin film transistors, photovoltaics, and light emitting diodes. However, the complex CP chemical structures and intramolecular interactions often make such control difficult to implement. We demonstrate here that cooperative combination of non-covalent interactions, including hydrogen bonding, coordination interactions, and π-π interactions, etc., can be used to effectively define the morphology of CP blend films, in particular being able to achieve accurate spatial arrangement of nanoparticles within CP nanostructures. Through UV-vis absorption spectroscopy and transmission electron microscopy, we show strong attachment of fullerene molecules, CdSe quantum dots, and iron oxide nanoparticles, onto well-defined CP nanofibers. The resulting core/shell hybrid nanofibers exhibit well-defined donor/acceptor interface when employed in photovoltaic devices, which also contributes to enhanced charge separation and transport. These findings provide a facile new methodology of improving CP/nanoparticle interfacial properties and controlling blend morphology. The generality of this methodology demonstrated in current studies points to a new way of designing hybrid materials based on organic polymers and inorganic nanoparticles towards applications in modern electronic devices.
In recent years, investigations of the phase transition behavior of semiconducting nanoparticles under high pressure has attracted increasing attention due to their potential applications in sensors, electronics, and optics. However, current understanding of how the size of nanoparticles influences this pressure-dependent property is somewhat lacking. In particular, phase behaviors of semiconducting CdS nanoparticles under high pressure have not been extensively reported. Therefore, in this work, CdS nanoparticles of different sizes are used as a model system to investigate particle size effects on high-pressure-induced phase transition behaviors. In particular, 7.5, 10.6, and 39.7 nm spherical CdS nanoparticles are synthesized and subjected to controlled high pressures up to 15 GPa in a diamond anvil cell. Analysis of all three nanoparticles using in-situ synchrotron wide-angle X-ray scattering (WAXS) data shows that phase transitions from wurtzite to rocksalt occur at higher pressures than for bulk material. Bulk modulus calculations not only show that the wurtzite CdS nanomaterial is more compressible than rocksalt, but also that the compressibility of CdS nanoparticles depends on their particle size. Furthermore, sintering of spherical nanoparticles into nanorods was observed for the 7.5 nm CdS nanoparticles. Our results provide new insights into the fundamental properties of nanoparticles under high pressure that will inform designs of new nanomaterial structures for emerging applications.
Photocatalytic hydrogen production from water is a facile and clean approach to convert rich solar energy into chemical fuel. Developing efficient and robust catalysts to accelerate water-splitting speed is key. Porphyrins exist widely in green plants and are a key photosensitizer to absorb and transfer light energy to other parts of the photosynthesis system of plants. They are considered an ideal model to construct artificial photocatalysts for hot-carrier-mediated hydrogen production. This article discusses recent achievements in constructing porphyrin-based photocatalysts for hydrogen production, including porphyrin molecules, self-assembled porphyrins, metal–organic frameworks, conjugated porphyrin polymers, and hybrid nanomaterial-based photocatalysts. The design and synthesis principles, structure–property relationships, as well as urgent issues to be solved in the future for every type of photocatalyst are also discussed.
There has been widespread recent interest in self-assembly and synthesis of porphyrin and its derivatives-based ordered arrays aiming to emulate natural light-harvesting processes and energy storage. However, technologies that leverage the structural advantages of individual porphyrins have not been fully realized and have been limited by available synthesis methods. This article provides general perspectives on porphyrin and derivative chemistry, and discussions on surfactant-assisted cooperative self-assembly using amphiphilic surfactants and functional porphyrins and derivatives. The cooperative self-assembly amplifies the intrinsic advantages of individual porphyrins by engineering them into well-defined one-dimensional–three-dimensional (1D–3D) nanostructures. Surfactant-assisted self-assembly of amphiphilic surfactants and porphyrins has been utilized to form well-defined “micelle-like” nanostructures. Driven by intermolecular interactions, subsequent nucleation and growth confined within these nanostructures lead to the formation of 1D–3D ordered optically and electrically active nanomaterials with structure and function on multiple length scales.
Porphyrins are vital pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A recent study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. Here we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. The cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.
Controlling microscopic morphology of energetic materials is of significant interest for the improvement of their performance and production consistency. As an important insensitive high explosive material, triaminotrinitrobenzene (TATB) has attracted tremendous research effort for military grade explosives and propellants. In this study, a new, rapid and inexpensive synthesis method for monodispersed TATB microparticles based on micelle-confined precipitation was developed. Surfactant with proper hydrophilic-lipophilic balance value was found to be critical to the success of this synthesis. The morphology of the TATB microparticles can be tuned between quasi-spherical and faceted by controlling the speed of recrystallization.
Morphological control of energetic materials (EM) is highly desired because ill-defined morphology arising from variations in processing method and supplier make it impossible to reproducibly engineer their physicochemical properties. As the most powerful, non nuclear energetic material to date, 2,4,6,8,10,12-hexanitro -2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) has been the subject of significant interest for improved applications in military grade explosives. Here we report a new method for recrystallization of CL-20 from irregular bulk EMs using a surfactant assisted self-assembly process to produce uniform spherical micron-sized particles. Detailed electron microscopy studies indicate that surfactant plays a critical role in controlling CL-20 morphology. Combined X-ray diffraction and Raman spectroscopy results reveal that the resultant spherical CL-20 particles exhibit an orthorhombic β-phase crystal structure. This material is expected to display enhanced functional reproducibility due to its monodisperse nature as well as decreased shock sensitivity due to their sub-micron particle size.
We recently developed a vacuum assisted micelle confinement synthesis for spherical microparticles of CL-20 with outstanding monodispersity. These microparticles are promising energetic material for explosive devices with enhanced and predictable performances. In this work, to facilitate further development and application of this synthesis, the particle growth process was monitored by in-situ dynamic light scattering measurements. The result was interpreted by a finite element model to obtain critical parameters. These parameters were then used to predict the behavior and product quality of batch synthesis under various operation conditions.
A new quantum dot synthesis method based on metallic-block copolymer precursors was developed. The synthesis produced CdS QDs assembled into chains. This method provides a new model for the study of 1D QD chains to determine its effect on charge transport and optoelectronic coupling. This synthesis method was readily extended to other semiconductor materials including PbS and perovskites producing QDs of various shapes. It evidenced further promise of this synthesis method to assist in the assembly, shape and size control of various nanomaterials
Low dimensional lead halide perovskite particles are of tremendous interest due to their size-tunable band gaps, low exciton binding energy, high absorption coefficients, outstanding quantum and photovoltaic efficiencies. Herein we report a new solution-based synthesis of stabilized Cs4PbBr6 perovskite particles with high luminescence. This method requires only mild conditions and produces colloidal particles that are ideal for highly efficient solution-based device fabrications. The synthesized microstructures not only display outstanding luminescence quantum yield but also long term stability in atmospheric conditions. Partial halide substitutions were also demonstrated to extend photoluminescence spectra of the perovskite particles. This convenient synthesis and optical tunability of Cs4PbBr6 perovskite particles will be advantageous for future applications of optoelectronic advices.
In an effort to utilize their unique photoactive properties, porphyrin monomers were assembled into tetragonal microparticles by a surfactant-assisted neutralization method through the cooperative interactions between the porphyrin building blocks including π-π stacking, J-aggregation and metal-ligand coordination. Electron microscopy characterization in combination with x-ray diffraction confirmed the three-dimensional ordered tetragonal microstructures with stable crystalline frameworks and well defined external surface morphology. Optical absorption and fluorescence spectroscopy revealed enhanced absorbance properties as compared with the raw porphyrin material, favourable for chromophore excitation and energy transport. With active and responsive optical properties, these new porphyrin microparticles look to serve as promising components for a wide range of applications including sensing, diagnostics, solar cells, and optoelectronic devices.
Carbon nanodots (CDs) have generated enormous excitement because of their superiority in water solubility, chemical inertness, low toxicity, ease of functionalization and resistance to photobleaching. Here we report a facile thermal pyrolysis route to prepare CDs with high quantum yield (QY) using citric acid as the carbon source and ethylene diamine derivatives (EDAs) including triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and polyene polyamine (PEPA) as the passivation agents. We find that the CDs prepared from EDAs, such as TETA, TEPA and PEPA, show relatively high photoluminescence (PL) QY (11.4, 10.6, and 9.8%, respectively) at λex of 465 nm. The cytotoxicity of the CDs has been investigated through in vitro and in vivo bio-imaging studies. The results indicate that these CDs possess low toxicity and good biocompatibility. The unique properties such as the high PL QY at large excitation wave length and the low toxicity of the resulting CDs make them promising fluorescent nanoprobes for applications in optical bio-imaging and biosensing.
Precise control of structural parameters through nanoscale engineering to continuously tailor optical and electronic properties of functional nanomaterials remains an outstanding challenge. Previous work focused largely on chemical or physical interactions that occur under ambient pressures. In this article, we introduce a new pressure-directed assembly and fabrication method that uses a mechanical compressive force applied to nanoparticles (NPs) to induce structural phase transitions and consolidate new nanomaterials with precisely controlled structures and tunable properties. By manipulating NP coupling through external pressure instead of through chemistry, a reversible change in assembly structure and properties can be demonstrated. In addition, over a certain threshold, the external pressure forces these NPs into contact, allowing the formation and consolidation of one- to three-dimensional nanostructures. Through stress-induced NP assembly, unusual materials engineering and synthesis, in which morphology and architecture can be readily tuned to produce desired optical and electrical properties, appear feasible.
We report plasmon excitation in 3-dimensional, ordered, gold nanocrystal(NC) arrays using a prism coupler. The gold NCs are arranged in the silica host matrix in a face-centered cubic lattice with the mono-dispersion gold core size of ∼3 nm. We observed the collective optical behavior of the gold NC array and found a blue shift in the plasmon absorption peak with increasing gold volume fraction (Au loading). Plasmon resonance bands centered at 536, 530 and 520 nm are measured for gold NC arrays with gold loading factors of 0.25, 0.5 and 1.0, respectively. The corresponding angular spectra of the gold NC arrays show resonance angles at 60.3, 63.3 and 66.4 degree.
Highly ordered gold NC/silica films are synthesized by self-assembly of water-soluble gold nanocrystal micelles and soluble silica using a sol-gel spin-coating technique. The optical properties are analyzed using ellipsometry and ultraviolet-visible spectroscopy. The absorption spectra show a strong surface plasmon absorption band at ∼520 nm for all samples. Angular excitation spectra of the surface plasmon show a steep dip in the reflectivity curve at ∼65°. Charge transport behavior of the films is examined using metal-oxide-semiconductor (MOS) structures.MOS capacitor samples exhibit charge storage with discharge behavior dominated by electron transport within the gold NC arrays.
The ability to engineer ordered arrays of objects on multiple length scales has potential for applications such as microelectronics, sensors, wave guides, and photonic lattices with tunable band gaps. Since the invention of surfactant templated mesoporous sieves in 1992, great progress has been made in controlling different mesophases in the form of powders, particles, fibers, and films. To date, although there have been several reports of patterned mesostructures, materials prepared have been limited to metal oxides with no specific functionality. For many of the envisioned applications of hierarchical materials in micro-systems, sensors, waveguides, photonics, and electronics, it is necessary to define both form and function on several length scales. In addition, the patterning strategies utilized so far require hours or even days for completion. Such slow processes are inherently difficult to implement in commercial environments. We present a series of new methods of producing patterns within seconds. Combining sol-gel chemistry, Evaporation-Induced Self-Assembly (EISA), and rapid prototyping techniques like pen lithography, ink-jet printing, and dip-coating on micro-contact printed substrates, we form hierarchically organized silica structures that exhibit order and function on multiple scales: on the molecular scale, functional organic moieties are positioned on pore surfaces, on the mesoscale, mono-sized pores are organized into 1-, 2-, or 3-dimensional networks, providing size-selective accessibility from the gas or liquid phase, and on the macroscale, 2-dimensional arrays and fluidic or photonic systems may be defined. These rapid patterning techniques establish for the first time a link between computer-aided design and rapid processing of self-assembled nanostructures.
The ability to engineer ordered arrays of objects on multiple length scales has potential for applications such as microelectronics, sensors, wave guides, and photonic lattices with tunable band gaps. Since the invention of surfactant templated mesoporous sieves in 1992, great progress has been made in controlling different mesophases in the form of powders, particles, fibers, and films. To date, although there have been several reports of patterned mesostructures, materials prepared have been limited to metal oxides with no specific functionality. For many of the envisioned applications of hierarchical materials in micro-systems, sensors, waveguides, photonics, and electronics, it is necessary to define both form and function on several length scales. In addition, the patterning strategies utilized so far require hours or even days for completion. Such slowprocesses are inherently difficult to implement in commercial environments. We present a series of new methods of producing patterns within seconds. Combining sol-gel chemistry, Evaporation-Induced Self-Assembly (EISA), and rapid prototyping techniques like pen lithography, ink-jet printing, and dip-coating on micro-contact printed substrates, we form hierarchically organized silica structures that exhibit order and function on multiple scales: on the molecular scale, functional organic moieties are positioned on pore surfaces, on the mesoscale, mono-sized pores are organized into 1-, 2-, or 3-dimensional networks, providing size-selective accessibility from the gas or liquid phase, and on the macroscale, 2-dimensional arrays and fluidic or photonic systems may be defined. These rapid patterning techniques establish for the first time a link between computer-aided design and rapid processing of self-assembled nanostructures
Using a micro-Contact Printing (μ-CP) technique, substrates are prepared with patterns of hydrophilic, hydroxyl-terminated SAMs and hydrophobic methyl-terminated SAMs. Beginning with a homogeneous solution of silica, surfactant, ethanol, water, and functional silane, preferential ethanol evaporation during dip-coating, causes water enrichment and selective de-wetting of the hydrophobic SAMs. Correspondingly, film deposition occurs exclusively on the patterned hydrophilic SAMs. In addition, by co-condensation of tetrafunctional silanes (Si(OR)4) with tri-functional organosilanes ((RO)3Si (CH2)3NH2), we have selectively derived the silica framework with functional amine NH2 groups. A pH sensitive, micro-fluidic system was formed by further conjugation reactions with pH sensitive dye molecules.
Using a micro-Contact Printing (μ-CP) technique, substrates are prepared with patterns of hydrophilic, hydroxyl-terminated SAMs and hydrophobic methyl-terminated SAMs. Beginning with a homogeneous solution of silica, surfactant, ethanol, water, and functional silane, preferential ethanol evaporation during dip-coating, causes water enrichment and selective de-wetting of the hydrophobic SAMs. Correspondingly, film deposition occurs exclusively on the patterned hydrophilic SAMs. In addition, by co-condensation of tetrafunctional silanes (Si(OR)4) with tri-functional organosilanes ((RO)3Si(CH2)3NH2), we have selectively derived the silica framework with functional amine NH2 groups. A pH sensitive, micro-fluidic system was formed by further conjugation reactions with pH sensitive dye molecules.