Efficacy of a Digital Health Preventive Intervention for Adolescents With HIV or Sexually Transmitted Infections and Substance Use Disorder: Protocol for a Randomized Controlled Trial.

BACKGROUND: HIV or sexually transmitted infections remain a significant public health concern in the United States, with adolescents affected disproportionately. Adolescents engage in HIV/STI risk behaviors, including drug use and condomless sex, which increase the risk for HIV/STIs. At-risk adolescents, many of whom are racial minorities, experience HIV/STI disparities. Although at-risk adolescents are disproportionately affected by HIV/STI risk behaviors and infections and although the Centers for Disease Control and Prevention recommends routine HIV/STI testing for adolescents, relatively few adolescents report having ever been tested for HIV/STI. With expected increases in health clinic visits as a result of the Affordable Care Act combined with technological advances, health clinics and mobile health (mHealth), including apps, provide innovative contexts and tools to engage at-risk adolescents in HIV/STI prevention programs. Yet, there is a dearth of efficacious mHealth interventions in health clinics to prevent and reduce both condomless sex and drug use and increase HIV/STI testing for at-risk adolescents. OBJECTIVE: To address this gap in knowledge, we developed a theory-driven, culturally congruent mHealth intervention (hereon referred to as S4E [Storytelling 4 Empowerment]) that has demonstrated feasibility and acceptability in a clinical setting. The next step is to examine the preliminary efficacy of S4E on adolescent HIV/STI testing and risk behaviors. This goal will be accomplished by 2 aims: the first aim is to develop a cross-platform and universal version of S4E. The cross-platform and universal version of S4E will be compatible with both iOS and Android operating systems and multiple mobile devices, aimed at providing adolescents with ongoing access to the intervention once they leave the clinic, and the second aim is to evaluate the preliminary efficacy of S4E, relative to usual care control condition, in preventing or reducing drug use and condomless sex and increasing HIV/STI testing in a clinical sample of at-risk adolescents aged 14-21 years living in Southeast Michigan. METHODS: In this study, 100 adolescents recruited from a youth-centered community health clinic will be randomized via blocked randomization with random sequences of block sizes to one of the 2 conditions: S4E mHealth intervention or usual care. Theory-driven and culturally congruent, S4E is an mHealth adaptation of face-to-face storytelling for empowerment, which is registered with the Substance Abuse and Mental Health Services Administration's National Registry of Evidence-Based Programs and Practices. RESULTS: This paper describes the protocol of our study. The recruitment began on May 1, 2018. This study was registered on December 11, 2017, in ClinicalTrials.gov. All participants have been recruited. Data analysis will be complete by the end of March 2024, with study findings available by December 2024. CONCLUSIONS: This study has the potential to improve public health by preventing HIV/STI and substance use disorders. TRIAL REGISTRATION: ClinicalTrials.gov NCT03368456; https://clinicaltrials.gov/study/NCT03368456. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR1-10.2196/47216.

Innovations in nanosynthesis: emerging techniques for precision, scalability, and spatial control in reactions of organic molecules on solid surfaces.

The surface science-based approach to synthesising new organic materials on surfaces has gained considerable attention in recent years, owing to its success in facilitating the formation of novel 0D, 1D and 2D architectures. The primary mechanism used to date has been the catalytic transformation of small organic molecules through substrate-enabled reactions. In this Topical Review, we provide an overview of alternate approaches to controlling molecular reactions on surfaces. These approaches include light, electron and ion-initiated reactions, electrospray ionisation deposition-based techniques, collisions of neutral atoms and molecules, and superhydrogenation. We focus on the opportunities afforded by these alternative approaches, in particular where they may offer advantages in terms of selectivity, spatial control or scalability.

Plasma-enabled superhydrophobic coatings on mild steel.

This work demonstrates a new pathway to the direct on-surface fabrication of a superhydrophobic surface coating on mild steel. The coating was formed using dielectric barrier discharge (DBD) plasma to convert a liquid small-molecule precursor (1,2,4-tricholorobenzene) to a solid film via plasma-assisted on-surface polymerization. Plasma treatments were performed under a nitrogen atmosphere with a variety of power levels and durations. Samples were analysed by optical and scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, optical profilometry, contact angle measurement, and potentiodynamic polarisation tests. Wettability of the films varied with the plasma parameters, and through the inclusion of graphene nanoplatelets in the precursor. High-dose plasma exposures of the nanoplatelet-containing precursor created superhydrophobic films with water contact angles above 150°. Potentiodynamic polarisation tests revealed that the superhydrophobic coating provided little or no corrosion protection.

High quality epitaxial graphene on 4H-SiC by face-to-face growth in ultra-high vacuum.

Epitaxial graphene on SiC is the most promising substrate for the next generation 2D electronics, due to the possibility to fabricate 2D heterostructures directly on it, opening the door to the use of all technological processes developed for silicon electronics. To obtain a suitable material for large scale applications, it is essential to achieve perfect control of size, quality, growth rate and thickness. Here we show that this control on epitaxial graphene can be achieved by exploiting the face-to-face annealing of SiC in ultra-high vacuum. With this method, Si atoms trapped in the narrow space between two SiC wafers at high temperatures contribute to the reduction of the Si sublimation rate, allowing to achieve smooth and virtually defect free single graphene layers. We analyse the products obtained on both on-axis and off-axis 4H-SiC substrates in a wide range of temperatures (1300 °C-1500 °C), determining the growth law with the help of x-ray photoelectron spectroscopy (XPS). Our epitaxial graphene on SiC has terrace widths up to 10µm (on-axis) and 500 nm (off-axis) as demonstrated by atomic force microscopy and scanning tunnelling microscopy, while XPS and Raman spectroscopy confirm high purity and crystalline quality.

MAX-phase Derived Tin Diselenide for 2D/2D Heterostructures with Ultralow Surface/Interface Transport Barriers toward Li-/Na-ions Storage.

2D tin diselenide and its derived 2D heterostructures have delivered promising potentials in various applications ranging from electronics to energy storage devices. The major challenges associated with large-scale fabrication of SnSe2 crystals, however, have hindered its engineering applications. Herein, a tin-extraction synthetic method is proposed for producing large-size SnSe2 bulk crystals. In a typical synthesis, a Sn-containing MAX phase (V2 SnC) and a Se source are heat-treated under a reducing atmosphere, by which Sn is extracted from the V2 SnC phase as a rectified Sn source to form SnSe2 crystals in the cold zone. After the following liquid exfoliation, the obtained 2D SnSe2 nanosheets have a lateral size of a few centimeters and an atomic thickness. Furthermore, by coupling with 2D graphene to form 2D/2D SnSe2 /graphene heterostructured electrodes, as validated by theoretical calculation and experimental studies, the superior Li-/Na-ion storage performance with ultralow surface/interface ion transport barriers are achieved for rechargeable Li-/Na-ion batteries. This innovative synthetic strategy opens a new avenue for the large-scale synthesis of selenides and offers more options into the practical application of emerging 2D/2D heterostructure for electrochemical energy storage.

Antimicrobial adhesive films by plasma-enabled polymerisation of m-cresol.

This work reveals a versatile new method to produce films with antimicrobial properties that can also bond materials together with robust tensile adhesive strength. Specifically, we demonstrate the formation of coatings by using a dielectric barrier discharge (DBD) plasma to convert a liquid small-molecule precursor, m-cresol, to a solid film via plasma-assisted on-surface polymerisation. The films are quite appealing from a sustainability perspective: they are produced using a low-energy process and from a molecule produced in abundance as a by-product of coal tar processing. This process consumes only 1.5 Wh of electricity to create a 1 cm2 film, which is much lower than other methods commonly used for film deposition, such as chemical vapour deposition (CVD). Plasma treatments were performed in plain air without the need for any carrier or precursor gas, with a variety of exposure durations. By varying the plasma parameters, it is possible to modify both the adhesive property of the film, which is at a maximum at a 1 min plasma exposure, and the antimicrobial property of the film against Escherichia coli, which is at a maximum at a 30 s exposure.

Multistimulus-Responsive Graphene Oxide/Fe3O4/Starch Soft Actuators.

Soft actuators that respond to external stimuli like moisture, magnetism, light, and temperature have received tremendous attention owing to their promising potential in many frontier applications, including smart switches, soft robots, sensors, and artificial muscles. However, most of the conventional actuators can only be triggered by a solo stimulus and demand advanced manufacturing techniques that utilize expensive, hazardous, and synthetic raw materials. Herein, we design and fabricate a multiple stimuli-responsive actuator using graphene oxide, Fe3O4 nanoparticles, and tapioca starch via a water evaporation-induced self-assembly method. The resultant hybrid actuator exhibits a bending speed of ∼72° s-1 upon moisture exposure. Moreover, it can perform clockwise and counterclockwise rotations, linear motion, and magnetic object capture by regulating a magnetic field. As representative examples, the actuator is used to fabricate various smart devices such as smart curtains, biomimetic structures, and a smart gripper that undergo complex and consecutive motion under the influence of multiple stimuli.

Carbon Nanomaterials Modified Biomimetic Dental Implants for Diabetic Patients.

Dental implants are used broadly in dental clinics as the most natural-looking restoration option for replacing missing or highly diseased teeth. However, dental implant failure is a crucial issue for diabetic patients in need of dentition restoration, particularly when a lack of osseointegration and immunoregulatory incompetency occur during the healing phase, resulting in infection and fibrous encapsulation. Bio-inspired or biomimetic materials, which can mimic the characteristics of natural elements, are being investigated for use in the implant industry. This review discusses different biomimetic dental implants in terms of structural changes that enable antibacterial properties, drug delivery, immunomodulation, and osseointegration. We subsequently summarize the modification of dental implants for diabetes patients utilizing carbon nanomaterials, which have been recently found to improve the characteristics of biomimetic dental implants, including through antibacterial and anti-inflammatory capabilities, and by offering drug delivery properties that are essential for the success of dental implants.

Self-supporting covalent organic framework membranes synthesized through two different processes: solvothermal annealing and solvent vapor annealing.

Rigid, freestanding covalent organic framework (COF-1) membranes have been synthesized from 1,4-benzenediboronic acid (BDBA) precursors using two different approaches: room temperature solvent-vapour annealing (SVA) and solvothermal annealing (SA). Characterization of films using Fourier-transform infrared (FTIR) spectroscopy, x-ray diffraction (XRD), and various microscopies shows that the films obtained through the two different routes vary in their retained BDBA proportion, crystal size and macroscale morphology. Gas adsorption measurements give specific surface areas of 579 ± 7 m2 g-1 and 739 ± 11 m2 g-1 respectively, suggesting that the average porosity of these films is competitive with bulk-synthesized COF-1 particles. The films have a stratified structure, with a dense, thin top layer and a thicker, sponge-like base layer. Using nanoindentation, we measured the Young's modulus at the top surface of the SVA and SA films to be 3.64 ± 1.20 GPa and 3.33 ± 0.12 GPa respectively, with the smaller uncertainty for the SA film attributed to a more uniform morphology. These measurements provide useful experimental data pertaining to COF-1 mechanical properties, furnishing information relevant to the use of these free-standing membranes in applications such as gas filtration or storage.

Synthesis and characterization of WS2/graphene/SiC van der Waals heterostructures via WO3-x thin film sulfurization.

Van der Waals heterostructures of monolayer transition metal dichalcogenides (TMDs) and graphene have attracted keen scientific interest due to the complementary properties of the materials, which have wide reaching technological applications. Direct growth of uniform, large area TMDs on graphene substrates by chemical vapor deposition (CVD) is limited by slow lateral growth rates, which result in a tendency for non-uniform multilayer growth. In this work, monolayer and few-layer WS2 was grown on epitaxial graphene on SiC by sulfurization of WO3-x thin films deposited directly onto the substrate. Using this method, WS2 growth was achieved at temperatures as low as 700 °C - significantly less than the temperature required for conventional CVD. Achieving long-range uniformity remains a challenge, but this process could provide a route to synthesize a broad range of TMD/graphene van der Waals heterostructures with novel properties and functionality not accessible by conventional CVD growth.

Surface-confined single-layer covalent organic frameworks: design, synthesis and application.

Two-dimensional (2D) nanomaterials, such as graphene and single layer covalent organic frameworks (sCOFs) are being widely studied due to their unusual structure/property relationships. sCOFs typically feature atomic thickness, intrinsic nanoscale porosity and a crystalline lattice. Compared to other organic 2D materials, sCOFs exhibit major advantages including topological designation and constitutional tunability. This review describes the state of the art of surface-confined sCOFs, emphasizing reticular design, synthesis approaches, and key challenges related to improving quality and exploring applications.

Multiscale Plasma-Catalytic On-Surface Assembly.

Controlled modification of surfaces is one of the key pursuits of the nanoscience and nanotechnology fields, allowing for the fabrication of bespoke materials with targeted functionalities. However, many surface modifications currently require painstakingly precise and/or energy intensive processing to implement, and are thus limited in scope and scale. Here, a concept which can enhance the capacity for control of surfaces is introduced: plasma-assisted nucleation and self-assembly at atomic to nanoscales, scalable at atmospheric pressures.

Simple Method for Estimating the Surface Area of Layered Graphene-Based Thin Films.

Thin films, papers, or foils produced from graphene-based materials have been the focus of considerable research interest in recent years. They have a range of applications including energy storage, selective filtration of liquids, and gas storage. For all of these applications, the critical attribute of the films is their pore volume. However, there remains a considerable challenge around characterizing the accessible microscopic surface area of the materials in their intended state of application. In this work, an image-processing-based approach is presented for estimating the lower threshold of specific surface area for graphene-based films that have a typical multilayered structure. Canny edge detection is used together with tortuosity measurements to infer sheet areas from layer edges. The method serves as a simple independent characterization technique. Specific surface area values predicted for a range of similar films vary by less than 4× the reported values, which vary by >1.1×103 in range.

Planar Anchoring of C70 Liquid Crystals Using a Covalent Organic Framework Template.

The surface-induced anchoring effect is a well-developed technique to control the growth of liquid crystals (LCs). Nevertheless, a defined nanometer-scale template has never been used to induce the anchored growth of LCs with molecular building units. Scanning tunneling microscopy results at the solid/liquid interface reveal that a 2D covalent organic framework (COF-1) can offer an anchoring effect to template C70 molecules into forming several LC mesophases, which cannot be obtained under other conditions. Through comparison with the C60 system, a stepwise breakdown in ordering of C70 LC is observed. The process is described in terms of the effects of molecular anisotropy on the epitaxial growth of molecular crystals. The results suggest that using a surface-confined template to anchor the initial layer of LC molecules can be a modular and potentially broadly applicable approach for organizing molecular mesogens into LCs.

Cleaning up after the Party: Removing the Byproducts of On-Surface Ullmann Coupling.

Ullmann coupling is one of the most frequently employed methodologies for producing π-conjugated surface-confined polymers. One unfortunate side product of the reaction is the creation of metal halide islands formed from liberated halogen atoms. Following the coupling reaction, these halide islands can account for a large proportion of the substrate surface area and thus inhibit domain growth and effectively poison the catalyst. Here, we describe an efficient and reliable methodology for removing the halogen byproduct at room temperature by exposure to a beam of atomic hydrogen; this action removes the halogen atoms in a matter of minutes, with minimal impact to the polymer structure. We also find that it is possible under certain circumstances to preserve the pre-exposure epitaxy after removal of the halogen. This finding provides a convenient and straightforward technique for addressing the most often-cited drawback of the on-surface Ullman coupling methodology and provides access to a previously inaccessible parameter space for these types of experiments.

Adsorption, Deprotonation, and Decarboxylation of Isophthalic Acid on Cu(111).

The surface-assisted reaction of rationally designed organic precursors is an emerging approach toward fabricating atomically precise nanostructures. Recently, on-surface decarboxylation has attracted attention due to its volatile by-products, which tend to leave the surface during the reaction means only the desired products are retained on the surface. However, in addition to acting as the reactive site, the carboxylic acid groups play a vital role in the adsorption configuration of small-molecule molecular precursors and therefore in the reaction pathways. Here, scanning tunnelling microscopy (STM), synchrotron radiation photoelectron spectroscopy (SRPES), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have been employed to characterize the monodeprotonated, fully deprotonated, and decarboxylated products of isophthalic acid (IPA) on Cu(111). IPA is partially reacted (monodeprotonated) upon adsorption on Cu(111) at room temperature. Angular-dependent X-ray photoelectron spectroscopy reveals that IPA initially anchors to the surface via the carboxylate group. After annealing, the molecule fully deprotonates and reorients so that it anchors to the surface via both carboxylate groups in a bipodal configuration. NEXAFS confirms that the molecule is tilted upon adsorption and after full deprotonation. Following decarboxylation, the flat-lying molecule forms into oligomeric motifs on the surface. This work demonstrates the importance of molecular adsorption geometry for on-surface reactions.

Direct-write crosslinking in vacuum-deposited small-molecule films using focussed ion and electron beams.

Recent advances in helium ion microscopy (HIM) have enabled the use of fine-focused He+ beams to image and shape materials at the nanoscale. In addition to traditional ion milling, the beam can also be used to induce reactions, such as cross-linking, in films of organic molecules. Here, we compare the use of focused ion and electron beams to fabricate spatially-defined cross-linked features in nanometre-thick films of tetracene. Ion and electron beam treatments were performed using the focussed energetic beams in a HIM and a scanning electron microscope, respectively. The patterned samples were analysed by optical microscopy, HIM, atomic force microscopy and nanoindentation. For samples fabricated using both energetic beams, the total deposited particle dose could be used to modify the optical properties, thickness and hardness of the dosed regions. X-ray photoelectron spectroscopy revealed that the dosed regions exhibited a higher sp3 content, consistent with crosslinking; rinsing in solvent showed that the patterned regions were insoluble and could be isolated by removing the unmodified film through dissolution. These molecular nanopatterns demonstrate the promise for ultrahigh resolution chemical lithography, and for fabrication of nanocomponents with tailored physical properties.

A Review of Supercapacitors Based on Graphene and Redox-Active Organic Materials.

Supercapacitors are a highly promising class of energy storage devices due to their high power density and long life cycle. Conducting polymers (CPs) and organic molecules are potential candidates for improving supercapacitor electrodes due to their low cost, large specific pseudocapacitance and facile synthesis methods. Graphene, with its unique two-dimensional structure, shows high electrical conductivity, large specific surface area and outstanding mechanical properties, which makes it an excellent material for lithium ion batteries, fuel cells and supercapacitors. The combination of CPs and graphene as electrode material is expected to boost the properties of supercapacitors. In this review, we summarize recent reports on three different CP/graphene composites as electrode materials for supercapacitors, discussing synthesis and electrochemical performance. Novel flexible and wearable devices based on CP/graphene composites are introduced and discussed, with an eye to recent developments and challenges for future research directions.

Electron effective attenuation length in epitaxial graphene on SiC.

The inelastic mean free path (IMFP) for carbon-based materials is notoriously challenging to model, and moving from bulk materials to 2D materials may exacerbate this problem, making the accurate measurements of IMFP in 2D carbon materials critical. The overlayer-film method is a common experimental method to estimate IMFP by measuring electron effective attenuation length (EAL). This estimation relies on an assumption that elastic scattering effects are negligible. We report here an experimental measurement of electron EAL in epitaxial graphene on SiC using photoelectron spectroscopy over an electron kinetic energy range of 50-1150 eV. We find a significant effect of the interface between the 2D carbon material and the substrate, indicating that the attenuation length in the so-called 'buffer layer' is smaller than for free-standing graphene. Our results also suggest that the existing models for estimating IMFPs may not adequately capture the physics of electron interactions in 2D materials.

Film formation from plasma-enabled surface-catalyzed dehalogenative coupling of a small organic molecule.

This work demonstrates a new pathway to the direct on-surface fabrication of surface coatings by showing that application of a plasma can lead to dehalogenative coupling of small aromatic molecules at a catalytic surface. Specifically, we show that a room temperature, atmospheric pressure plasma can be used to fabricate a coating through a surface-confined dehalogenation reaction. Plasma treatments were performed using a dielectric barrier discharge (DBD) technique under pure nitrogen with a variety of power levels and durations. Samples were analysed by optical and helium ion microscopy (HIM), X-ray photoelectron spectroscopy (XPS), optical profilometry, and contact angle measurement. By varying the plasma parameters we could control the chemistry, morphology and roughness of the film. Surface wettability also varied with the plasma parameters, with high-dose plasmas leading to a hydrophobic surface with water contact angles up to 130°.