Poly(HEMA-co-HEMA-PFPA): Synthesis and preparation of stable micelles encapsulating imaging nanoparticles.

We report the preparation of stable micelles from random copolymers of 2-hydroxyethyl methacrylate (HEMA) and perfluorophenyl azide (PFPA)-derivatized HEMA (HEMA-PFPA). The copolymers were synthesized by RAFT polymerization at room temperature under mild conditions without affecting the azide functionality. Upon addition of water to the copolymer solution in DMSO, the random copolymers self-assembled into micelles even at the percentage of HEMA-PFPA as low as 4.5%. The size of the micelles can be controlled by the molecular weight and the concentration of the copolymer, and the percentage of HEMA-PFPA in the copolymer. In addition, iron oxide nanoparticles and quantum dots were successfully encapsulated into the micelles with high encapsulation efficiency (∼80%). These nanoparticles, which were hydrophobic and formed agglomerates in water, became fully dispersed after encapsulating into the micelles. The micelles were stable and the size remained unchanged for at least 6months.

Magnetic Multivalent Trehalose Glycopolymer Nanoparticles for the Detection of Mycobacteria.

A multivalent trehalose-grafted poly(lactic acid) is synthesized and encapsulated with iron oxide magnetic nanoparticles. The magnetic micelles interact with Mycobacterium smegmatis to form orange clusters. Very little particle interaction is found on Staphylococcus epidermidis 35984 or Escherichia coli ORN 208. The presented new approach to the detection of mycobacteria does not require molecular biology reagents or sophisticated instruments.

Enzyme classification using complex dynamic hemithioacetal systems.

A complex dynamic hemithioacetal system was generated for the evaluation of lipase reactivities in organic media. In combination with pattern recognition methodology, twelve different lipases were successfully classified into four distinct groups following their reaction selectivities and reactivities. A probe lipase was further categorized using the training matrix with predicted reactivity.

Fabrication of carbohydrate microarrays on a poly(2-hydroxyethyl methacrylate)-based photoactive substrate.

We report the fabrication of carbohydrate microarrays on a photoactive polymer, poly(HEMA-co-HEMA-PFPA), synthesized by RAFT copolymerization of 2-hydroxyethyl methacrylate (HEMA) and perfluorophenyl azide (PFPA)-derivatized HEMA (HEMA-PFPA). PFPA allows the covalent immobilization of carbohydrates whereas the HEMA polymer provides an antifouling surface, thus the microarrays can be used directly without pretreating the array with a blocking agent. The microarrays were prepared by spin-coating the polymer followed by printing the carbohydrates. Subsequent irradiation simultaneously immobilized the carbohydrates and crosslinked the polymer matrix. The obtained 3D carbohydrate microarrays showed enhanced fluorescence signals upon treating with a fluorescent lectin in comparison with a 2D microarray. The signals were acquired at a lower lectin concentration and a shorter incubation time. When treated with E. coli bacteria, the carbohydrate microarray showed results that were consistent with their binding patterns.

Selective targeting of Mycobacterium smegmatis with trehalose-functionalized nanoparticles.

Silica and iron oxide nanoparticles with sizes ranging from 6 to 40 nm were functionalized with trehalose. The trehalose-conjugated nanoparticles showed strong interactions with Mycobacterium smegmatis (M. smegmatis) and minimal interactions with macrophage (RAW 264.7) or A549 cells. In addition, trehalose-conjugated silica nanoparticles selectively interacted with M. smegmatis on M. smegmatis-treated A549 cells, demonstrating high potential of trehalose in developing targeted therapy for treating mycobacterial infection.

Synthesis of multifunctional cellulose nanocrystals for lectin recognition and bacterial imaging.

Multifunctional cellulose nanocrystals have been synthesized and applied as a new type of glyconanomaterial in lectin binding and bacterial imaging. The cellulose nanocrystals were prepared by TEMPO-mediated oxidation and acidic hydrolysis, followed by functionalization with a quinolone fluorophore and carbohydrate ligands. The cellulose nanocrystals were subsequently applied in interaction studies with carbohydrate-binding proteins and in bacterial imaging. The results show that the functional cellulose nanocrystals could selectively recognize the corresponding cognate lectins. In addition, mannosylated nanocrystals were shown to selectively interact with FimH-presenting E. coli, as detected by TEM and confocal fluorescence microscopy. These glyconanomaterials provide a new application of cellulose nanocrystals in biorecognition and imaging.

A general method for the fabrication of graphene-nanoparticle hybrid material.

We describe a simple and general approach to conjugate nanoparticles on pristine graphene. The method takes advantage of the high reactivity of perfluorophenyl nitrene towards the C[double bond, length as m-dash]C bonds in graphene, where perfluorophenyl azide-functionalized nanoparticles are conjugated to pristine graphene through the [2+1] cycloaddition reaction by a fast photoactivation.

Glycan-functionalized fluorescent chitin nanocrystals for biorecognition applications.

A new platform based on chitin nanocrystals has been developed for biorecognition applications. TEMPO-oxidized chitin nanocrystals (TCNs) were labeled with a fluorescent imidazoisoquinolinone dye, and simultaneously conjugated with carbohydrate ligands, resulting in dually functionalized TCNs. The biorecognition properties of the nanocrystals were probed with lectins and bacteria, resulting in selective interactions with their corresponding cognate carbohydrate-binding proteins, as visualized by optical, fluorescence, STEM, and TEM imaging. This represents a new approach to multifunctional nanomaterials based on naturally occurring polymers, holding high potential for biomedical applications.

Classification of lectins by pattern recognition using glyconanoparticles.

Carbohydrate-functionalized gold nanoparticles were employed to differentiate plant-legume lectins using a statistical analysis method of linear discriminant analysis (LDA). Various carbohydrates were conjugated on gold nanoparticles, and the resulting glyconanoparticles were treated with lectins. Changes in the localized surface plasmon resonance of the glyconanoparticles upon lectin binding were recorded, and the data were subjected to LDA. Results showed that the glyconanoparticles successfully differentiated all lectins.

Photoconjugation of molecularly imprinted polymer with magnetic nanoparticles.

Because of their synthetic accessibility, molecularly imprinted polymer (MIP) nanoparticles are ideal building blocks for preparing multifunctional composites. In this work, we developed a general photocoupling chemistry to enable simple conjugation of MIP nanoparticles with inorganic magnetic nanoparticles. We first synthesized MIP nanoparticles using propranolol as a model template and perfluorophenyl azide-modified silica-coated magnetic nanoparticles. Using a simple photoactivation followed by facile purification with a magnet, we obtained magnetic composite particles that showed selective uptake of propranolol. We characterized the nanoparticles and composite materials using FT-IR, TEM, fluorescence spectroscopy, and radioligand binding analysis. Through the high molecular selectivity of the magnetic composite, we demonstrated the nondestructive feature and the high efficiency of the photocoupling chemistry. The versatile photoconjugation method developed in this work should also be very useful for combining organic MIPs with other inorganic nanoparticles to enable new chemical sensors and high efficiency photocatalysts.

Maltoheptaose promotes nanoparticle internalization by Escherichia coli.

Nanoparticles conjugated with d-maltoheptaose (G7) showed a striking increase in the internalization by Escherichia coli. This applies to strains with and without the maltodextrin transport channel and particles ranging from a few to a hundred nanometers.