Locally altering the electronic properties of graphene by nanoscopically doping it with Rhodamine 6G.

We show that Rhodamine 6G (R6G), patterned by dip-pen nanolithography on graphene, can be used to locally n-dope it in a controlled fashion. In addition, we study the transport and assembly properties of R6G on graphene and show that in general the π-π stacking between the aromatic components of R6G and the underlying graphene drives the assembly of these molecules onto the underlying substrate. However, two distinct transport and assembly behaviors, dependent upon the presence or absence of R6G dimers, have been identified. In particular, at high concentrations of R6G on the tip, dimers are transferred to the substrate and form contiguous and stable lines, while at low concentrations, the R6G is transferred as monomers and forms patchy, unstable, and relatively ill-defined features. Finally, Kelvin probe force microscopy experiments show that the local electrostatic potential of the graphene changes as function of modification with R6G; this behavior is consistent with local molecular doping, highlighting a path for controlling the electronic properties of graphene with nanoscale resolution.

Gold nanotip array for ultrasensitive electrochemical sensing and spectroscopic monitoring.

A gold nanotip array platform with a combination of ultrasensitive electrochemical sensing and spectroscopic monitoring capability is reported. Adenosine triphosphate is detected down to 1 pM according to the impedance changes in response to aptamer-specific binding. Furthermore, the local molecular information can be monitored at the individual plasmonic nanotips, and hence provide the capability for a better understanding of complex biological processes.

Collagen-cellulose composite thin films that mimic soft-tissue and allow stem-cell orientation.

Mechanical properties of collagen films are less than ideal for biomaterial development towards musculoskeletal repair or cardiovascular applications. Herein, we present a collagen-cellulose composite film (CCCF) compared against swine small intestine submucosa in regards to mechanical properties, cell growth, and histological analysis. CCCF was additionally characterized by FE-SEM, NMR, mass spectrometry, and Raman Microscopy to elucidate its physical structure, collagen-cellulose composition, and structure activity relationships. Mechanical properties of the CCCF were tested in both wet and dry environments, with anisotropic stress-strain curves that mimicked soft-tissue. Mesenchymal stem cells, human umbilical vein endothelial cells, and human coronary artery smooth muscle cells were able to proliferate on the collagen films with specific cell orientation. Mesenchymal stem cells had a higher proliferation index and were able to infiltrate CCCF to a higher degree than small intestine submucosa. With the underlying biological properties, we present a collagen-cellulose composite film towards forthcoming biomaterial-related applications.

Graphene-based composites.

Graphene has attracted tremendous research interest in recent years, owing to its exceptional properties. The scaled-up and reliable production of graphene derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), offers a wide range of possibilities to synthesize graphene-based functional materials for various applications. This critical review presents and discusses the current development of graphene-based composites. After introduction of the synthesis methods for graphene and its derivatives as well as their properties, we focus on the description of various methods to synthesize graphene-based composites, especially those with functional polymers and inorganic nanostructures. Particular emphasis is placed on strategies for the optimization of composite properties. Lastly, the advantages of graphene-based composites in applications such as the Li-ion batteries, supercapacitors, fuel cells, photovoltaic devices, photocatalysis, as well as Raman enhancement are described (279 references).

OWL-based nanomasks for preparing graphene ribbons with sub-10 nm gaps.

We report a simple and highly efficient method for creating graphene nanostructures with gaps that can be controlled on the sub-10 nm length scale by utilizing etch masks comprised of electrochemically synthesized multisegmented metal nanowires. This method involves depositing striped nanowires with Au and Ni segments on a graphene-coated substrate, chemically etching the Ni segments, and using a reactive ion etch to remove the graphene not protected by the remaining Au segments. Graphene nanoribbons with gaps as small as 6 nm are fabricated and characterized with atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. The high level of control afforded by electrochemical synthesis of the nanowires allows us to specify the dimensions of the nanoribbon, as well as the number, location, and size of nanogaps within the nanoribbon. In addition, the generality of this technique is demonstrated by creating silicon nanostructures with nanogaps.

Controlled growth of single-walled carbon nanotubes on patterned substrates.

Single-walled carbon nanotubes (SWCNTs) have attracted great interest in the last two decades because of their unique electrical, optical, thermal, mechanical properties, etc. One major research field of SWCNTs is the controlled growth of them from the patterned catalysts on substrates, since the integration of SWCNTs into nanoelectronics and other devices requires well-organized SWCNT arrays. This tutorial review describes the commonly used lithographic techniques to pattern catalysts used for controlled growth of SWCNTs, specifically confined to the horizontal direction. Advantages and disadvantages of each method will be briefly discussed. Applications of the SWCNT arrays grown from the catalyst patterns will also be introduced.

Fast formation of SnO2 nanoboxes with enhanced lithium storage capability.

SnO(2) nanoboxes with uniform morphology, good structural stability, and tunable interior volume can be facilely synthesized by template-engaged coordinating etching of pregrown Cu(2)O nanocubes at room temperature. When evaluated for their lithium storage properties, these SnO(2) nanoboxes manifest improved capacity retention.

Chemically functionalized surface patterning.

Patterning substrates with versatile chemical functionalities from micro- to nanometer scale is a long-standing and interesting topic. This review provides an overview of a range of techniques commonly used for surface patterning. The first section briefly introduces conventional micropatterning tools, such as photolithography and microcontact printing. The second section focuses on the currently used nanolithographic techniques, for example, scanning probe lithography (SPL), and their applications in surface patterning. Their advantages and disadvantages are also demonstrated. In the last section, dip-pen nanolithography (DPN) is emphatically illustrated, with a particular stress on the patterning and applications of biomolecules.

Micro-/nano-engineered cellular responses for soft tissue engineering and biomedical applications.

The development of biomedical devices and reconstruction of functional ex vivo tissues often requires the need to fabricate biomimetic surfaces with features of sub-micrometer precision. This can be achieved with the advancements in micro-/nano-engineering techniques, allowing researchers to manipulate a plethora of cellular behaviors at the cell-biomaterial interface. Systematic studies conducted on these 2D engineered surfaces have unraveled numerous novel findings that can potentially be integrated as part of the design consideration for future 2D and 3D biomaterials and will no doubt greatly benefit tissue engineering. In this review, recent developments detailing the use of micro-/nano-engineering techniques to direct cellular orientation and function pertinent to soft tissue engineering will be highlighted. Particularly, this article aims to provide valuable insights into distinctive cell interactions and reactions to controlled surfaces, which can be exploited to understand the mechanisms of cell growth on micro-/nano-engineered interfaces, and to harness this knowledge to optimize the performance of 3D artificial soft tissue grafts and biomedical applications.

Graphene-based materials: synthesis, characterization, properties, and applications.

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.

One-pot encapsulation of luminescent quantum dots synthesized in aqueous solution by amphiphilic polymers.

A simple one-pot polymer encapsulation method is developed for group II-VI semiconductor quantum dots (QDs) synthesized in aqueous solution. The micelles of amphiphilic polymers, such as octadecylamine-modified poly(acrylic acid), capture and encapsulate the QDs when the original hydrophilic ligands, namely 3-mercaptopropionic acid (MPA), capped on the CdTe/CdS core/shell QDs are partially or fully exchanged by the hydrophobic ligands, 1-dodecanethiol. The molar ratio of the amphiphilic polymer to QDs plays a crucial role in determining the final morphology of the encapsulated structures, including the number of QDs encapsulated in one polymeric micelle. Importantly, the polymer coating significantly improves the optical properties of the QDs, which enhances the photoluminescence quantum yield by about 50%. Furthermore, the photostability of the amphiphilic polymer-coated QDs is much better than that of the synthesized QDs capped with MPA.

Chemical reaction between Ag nanoparticles and TCNQ microparticles in aqueous solution.

The chemical reaction between Ag nanoparticles (Ag NPs) and 7,7',8,8'- tetracycanoquinodimethane (TCNQ) microparticles (MPs) in aqueous solution for the formation of Ag-NP-decorated Ag-TCNQ nanowires is reported. Based on the results obtained by UV-vis spectroscopy and scanning electron microscopy (SEM), it is proposed that the reaction between Ag NPs and TCNQ MPs includes three stages, namely, aggregation of NPs and MPs, diffusion and reaction between NPs and MPs, and formation of Ag-TCNQ nanowires. The as-synthesized semiconducting Ag-TCNQ nanowires show good performance in nonvolatile memory devices with multiple write-read-erase-read (WRER) cycles in air.

Effect of cell-seeding density on the proliferation and gene expression profile of human umbilical vein endothelial cells within ex vivo culture.

BACKGROUND AIMS: Characterization of endothelial cell-biomaterial interaction is crucial for the development of blood-contacting biomedical devices and implants. However, a crucial parameter that has largely been overlooked is the cell-seeding density. METHODS: This study investigated how varying cell-seeding density influences human umbilical vein endothelial cell (HUVEC) proliferation on three different substrata: gelatin, tissue culture polystyrene (TCPS) and poly-l-lactic acid (PLLA). RESULTS: The fastest proliferation was seen on gelatin, followed by TCPS and PLLA, regardless of seeding density. On both TCPS and gelatin, maximal proliferation was attained at an initial seeding density of 1000 cells/cm(2). At seeding densities above and below 1000 cells/cm(2), the proliferation rate decreased sharply. On PLLA, there was a decrease in cell numbers over 7 days of culture, below a certain threshold seeding density (c. 2500-3000 cells/cm(2)), which meant that some of the cells were dying off rather than proliferating. Above this threshold seeding density, HUVEC displayed slow proliferation. Subsequently, quantitative real-time polymerase chain reaction (RT-qPCR) analysis of eight gene markers associated with adhesion and endothelial functionality (VEGF-A, integrin-α5, VWF, ICAM1, ICAM2, VE-cadherin, endoglin and PECAM1) was carried out on HUVEC seeded at varying densities on the three substrata. A significant downregulation of gene expression was observed at an ultralow cell-seeding density of 100 cells/cm(2). This was accompanied by an extremely slow proliferation rate, probably because of an acute lack of intercellular contacts and paracrine signaling. CONCLUSION: Hence, this study demonstrates that seeding density has a profound effect on the proliferation and gene expression profile of endothelial cells seeded on different biomaterial surfaces.

A new insight for an old system: protein-PEG colocalization in relation to protein release from PCL/PEG blends.

Quantification of protein-polymer colocalization in a phase-separated polymer blend gives important insights into the protein release mechanism. Here, we report on the first visualization of protein-poly(ethylene glycol) (protein-PEG) colocalization in poly(ε-caprolactone)/poly(ethylene glycol) (PCL/PEG) blend films using a combined application of confocal Raman mapping and confocal laser scanning microscopy (CLSM) imaging. The degree of protein-PEG colocalization was further quantified via a novel image processing technique. This technique also allowed us to characterize the 3-D protein distribution within the films. Our results showed that the proteins were homogeneously distributed within the film matrix, independent of PEG content. However, the degree of protein-PEG colocalization was inversely proportional to PEG content, ranging from 65 to 94%. This quantitative data on protein-PEG colocalization was used along with in vitro PEG leaching profile to construct a predictive model for overall protein release. Our prediction matched well with the experimental protein release profile, which is characterized by an initial burst release and a subsequent slower diffusional release. More importantly, the success of this predictive model has highlighted the influence of protein-PEG colocalization on the protein release mechanism.

Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

Cytotoxicity of zinc oxide (ZnO) nanoparticles is influenced by cell density and culture format.

A parameter that has often been overlooked in cytotoxicity assays is the density and confluency of mammalian cell monolayers utilized for toxicology screening. Hence, this study investigated how different cell seeding densities influenced their response to cytotoxic challenge with ZnO nanoparticles. Utilizing the same volume (1 ml per well) and concentration range (5-40 µg/ml) of ZnO nanoparticles, contradictory results were observed with higher-density cell monolayers (BEAS-2B cells) obtained either by increasing the number of seeded cells per well (50,000 vs. 200,000 cells per well of 12-well plate) or by seeding the same numbers of cells (50,000) within a smaller surface area (12-well vs. 48-well plate, 4.8 vs. 1.2 cm(2), respectively). Further experiments demonstrated that the data may be skewed by inconsistency in the mass/number of nanoparticles per unit area of culture surface, as well as by inconsistent nanoparticle to cell ratio. To keep these parameters constant, the same number of cells (50,000 per well) were seeded on 12-well plates, but with the cells being seeded at the edge of the well for the experimental group (by tilting the plate) to form a dense confluent monolayer, as opposed to a sparse monolayer for the control group seeded in the conventional manner. Utilizing such an experimental set-up for the comparative evaluation of four different cell lines (BEAS-2B, L-929, CRL-2922 and C2C12), it was observed that the high cell density monolayer was consistently more resistant to the cytotoxic effects of ZnO nanoparticles compared to the sparse monolayer for all four different cell types, with the greatest differences being observed above a ZnO concentration of 10 µg/ml. Hence, the results of this study demonstrate the need for the standardization of cell culture protocols utilized for toxicology screening of nanoparticles, with respect to cell density and mass/number of nanoparticles per unit area of culture surface.

Seeding density matters: extensive intercellular contact masks the surface dependence of endothelial cell-biomaterial interactions.

The effects of seeding density have often been overlooked in evaluating endothelial cell-biomaterial interactions. This study compared the cell attachment and proliferation characteristics of endothelial cells on modified poly (L: -lactic acid) (PLLA) films conjugated to gelatin and chitosan at low and high seeding densities (5,000 and 50,000 cells/cm(2)). During the early stage (2 h) of cell-biomaterial interaction, a low seeding density enabled us to observe the intrinsic surface-dependent differences in cell attachment capacity and morphogenesis, whereas extensive intercellular interactions at high seeding density masked differences between substrates and improved cell attachment on low-affinity substrates. During the later stage of cell-biomaterial interaction over 7-days of culture, the proliferation rate was found to be surface-dependent at low seeding density, whereas this surface-dependent difference was not apparent at high seeding density. It is recommended that low seeding density should be utilized for evaluating biomaterial applications where EC density is likely to be low, such as in situ endothelialization of blood-contacting devices.

Clinical Diagnostic Study of a Novel Injection Molded Swab for SARS-Cov-2 Testing.

INTRODUCTION: The gold standard for COVID-19 diagnosis is currently a real-time reverse transcriptase polymerase chain reaction (RT-PCR) to detect SARS-CoV-2. This is most commonly performed on respiratory secretions obtained via a nasopharyngeal swab. Due to supply chain limitations and high demand worldwide because of the COVID-19 pandemic, access to commercial nasopharyngeal swabs has not been assured. 3D printing methods have been used to meet the shortfall. For longer-term considerations, 3D printing may not compare well with injection molding as a production method due to the challenging scalability and greater production costs of 3D printing. METHODS: To secure sufficient nasopharyngeal swab availability for our national healthcare system, we designed a novel injection molded nasopharyngeal swab (the IM2 swab). We performed a clinical diagnostic study comparing the IM2 swab to the Copan FLOQSwab. Forty patients with a known diagnosis of COVID-19 and 10 healthy controls were recruited. Paired nasopharyngeal swabs were obtained from the same nostril of each participant and tested for SARS-CoV-2 by RT-PCR. RESULTS: When compared to the Copan FLOQswab, results from the IM2 swab displayed excellent overall agreement and positive percent agreement of 96.0% and 94.9%, respectively. There was no significant difference in mean RT-PCR cycle threshold values for the ORF1ab (28.05 vs. 28.03, p = 0.97) and E-gene (29.72 vs. 29.37, p = 0.64) targets, respectively. We did not observe any significant adverse events and there was no significant difference in patient-reported pain. CONCLUSION: In summary, the IM2 nasopharyngeal swab is a clinically safe, highly accurate option to commercial nasopharyngeal swabs.

Postchemistry of organic particles: when TTF microparticles meet TCNQ microstructures in aqueous solution.

Through the use of preformed tetrathiafulvalene (TTF) particles and 7,7',8,8'-tetracyanoquinodimethane (TCNQ) microstructures as starting materials, the postchemistry of organic particles has been demonstrated for the first time in aqueous solution. The as-synthesized TTF-TCNQ nanowires show stable performance in organic nonvolatile memory devices with multiple write-read-erase-read cycles in air.

Engineering nonspherical hollow structures with complex interiors by template-engaged redox etching.

Despite the significant advancement in making hollow structures, one unsolved challenge in the field is how to engineer hollow structures with specific shapes, tunable compositions, and desirable interior structures. In particular, top-down engineering the interiors inside preformed hollow structures is still a daunting task. In this work, we demonstrate a facile approach for the preparation of a variety of uniform hollow structures, including Cu(2)O@Fe(OH)(x) nanorattles and Fe(OH)(x) cages with various shapes and dimensions by template-engaged redox etching of shape-controlled Cu(2)O crystals. The composition can be readily modulated at different structural levels to generate other interesting structures such as Cu(2)O@Fe(2)O(3) and Cu@Fe(3)O(4) rattles, as well as Fe(2)O(3) and Fe(3)O(4) cages. More remarkably, this strategy enables top-down engineering the interiors of hollow structures as demonstrated by the fabrication of double-walled nanorattles and nanoboxes, and even box-in-box structures. In addition, this approach is also applied to form Au and MnO(x) based hollow structures.