Zoledronate (Zol) is a bone-preserving/ anti-tumoral drug that is widely used for the treatment of many cancers including spinal bone metastases. High systemic Zol doses required to elicit an adequate effect in the spine often lead to significant side effects, limiting its prolonged use and effectiveness. Here, we aim to provide an alternative strategy to locally deliver Zol at the tumor site. We show that nanoporous 3D-printed scaffolds can be loaded with Zol and possess the ability to release Zol (10-28%) over a sustained period. Additionally, we demonstrate that Zol-impregnated scaffolds, mostly Gel Lay, impair the proliferation of the prostate cancer cell line LAPC4 and the prostate-induced bone metastasis cells in vitro. 3D-printed nanoporous polymers offer a novel and versatile opportunity for potential local delivery of drugs in future clinical settings. These polymers can decrease systemic exposure and related side effects of Zol while at the same time concentrating the drug effect at the tumor site thereby inhibiting tumor proliferation. Also, these scaffolds could be co-printed or coupled with other materials to produce custom implants that offer better structural support for bone growth at the tumor site following resection.

The need for hollow microneedle arrays is important for both drug delivery and wearable sensor applications; however, their fabrication poses many challenges. Hollow metal microneedle arrays residing on a flexible metal foil substrate were created by combining additive manufacturing, micromolding, and electroplating approaches in a process we refer to as electromolding. A solid microneedle with inward facing ledge was fabricated with a two photon polymerization (2PP) system utilizing laser direct write (LDW) and then molded with polydimethylsiloxane. These molds were then coated with a seed layer of Ti/Au and subsequently electroplated with pulsed deposition to create hollow microneedles. An inward facing ledge provided a physical blocking platform to restrict deposition of the metal seed layer for creation of the microneedle bore. Various ledge sizes were tested and showed that the resulting seed layer void could be controlled via the ledge length. Mechanical properties of the PDMS mold was adjusted via the precursor ratio to create a more ductile mold that eliminated tip damage to the microneedles upon removal from the molds. Master structures were capable of being molded numerous times and molds were able to be reused. SEM/EDX analysis showed that trace amounts of the PDMS mold were transferred to the metal microneedle upon removal. The microneedle substrate showed a degree of flexibility that withstood over 100 cycles of bending from side to side without damaging. Microneedles were tested for their fracture strength and were capable of puncturing porcine skin and injecting a dye.

High resolution (< 1 µm) computed tomography is an attractive tool in materials research due to its ability to non-destructively visualize the three-dimensional internal microstructures of the material. Recently, this technique has been further empowered by adding a fourth (temporal) dimension to study the time-lapse material response under load. Such studies are referred to as four-dimensional or in situ testing. In this snapshot review, we highlight three representative examples of in situ testing using synchrotron radiation computed tomography (SRCT) for composites failure analysis, measurement of local corrosion rate in alloys, and visualization and quantification of electrochemical reactions in lithium-ion batteries, as well as forward-looking integration of machine learning with in situ CT. Lastly, the future opportunities and challenges of in situ SRCT testing are discussed.

Using ab initio simulation, we study a ferroelectric layer of a few nanometers made of hafnia (HfO2) under the influence of Si doping with TiN electrodes. We evaluate the orthorhombic phase of Pca21 symmetry, its ferroelectric switching and the incidence of doping with silicon. We show that the ferroelectric switching can involve a 90° characteristic angle with corresponding activation energy which is lowered by a factor three due to Si doping at 3% at. A full MFM (Metal-Ferroelectric-Metal) model is derived in order to simulate finite-size effects. This model is compatible with a reversal of a polar HfO2:Si with a (111) preferential orientation. Validity and usefulness of such a model are discussed for ferroelectric devices optimization.

Age-related macular degeneration (AMD), a retinal degenerative disease that results in a continuous degeneration of photoreceptors in the retina, which eventually leads to complete blindness. One approach to combat AMD is through the use of artificially implantable photodetectors that are physically placed on the retina. Interestingly, 2D materials such as photosensitive and semiconducting molybdenum disulfide (MoS2) and electrically conducting graphene have recently received tremendous promise due to their unique photonic and optoelectronic properties and their potential in various types of micro and nano-devices. In this study, a highly biocompatible 2D graphene-MoS2 photodetectors on a flexible polyimide substrate were designed, fabricated using inkjet printing to form photosensitive pixels and tested as a function of photo intensity and strain. The inkjet printed 2D heterostructure devices were photoresponsive and the photocurrent scaled proportionally with the incident light intensity, exhibiting a photoresponsivity R ∼ 0.30 A/W at room temperature. The strain-dependent measurements of photocurrent with bending showed a photocurrent of Iph ∼ 1.16 μA with strain levels for curvature up to ∼ 0.262 cm-1. Inkjet printed graphene and MoS2 inks were also characterized using techniques such as Raman Spectroscopy, Photoluminescence (PL) and Scanning Electron Microscopy (SEM).

We present a new class of bioinspired nanomaterials that are stabilized by a combination of covalent and hydrogen bonds. Prior work by others has shown that cyclic peptides can self-assemble to form supramolecular assemblies through backbone-backbone hydrogen bonding. To improve upon this molecular architecture, we develop a synthesis route to polymerize cyclic peptides and form a linear polymer chain that can transition between a rigid nanorod and an unfolded conformation. For a cyclic peptide polymer containing amine-terminated side chains on each ring, we demonstrate self-assembly can be triggered in aqueous solutions by varying the pH. We measure the elastic modulus of the rigid nanorods to be ca. 50 GPa, which is comparable to our molecular dynamics (MD) prediction (ca. 64 GPa). Our results highlight the uniqueness of our molecular architecture, namely their exemplary toughness (up to 3 GJ m-3), in comparison to other cyclic peptide-based assemblies. Finally, we demonstrate amphiphilic cyclic β-peptides are capable of inhibiting the growth of gram-negative and gram-positive bacteria.

This work describes exploration of mitigating the parasitic amorphous alumina (Al2O3) shell of aluminum nanoparticles (n-Al) and modifying the surface using different plasmas, leading to n-Al with thinner shell and different coatings including carbons and oxidizing salt called aluminum iodate hexahydrate (AIH), respectively. The approach exploits a prototype atmospheric non-thermal plasma reactor with dielectric barrier discharge (DBD) configuration for nanoparticle surface modifications using n-Al of 80 nm average diameter as an example. Preliminary results indicate that the amorphous Al2O3 shell surrounding the active aluminum core can be mitigated with inert plasmas by as much as 40% using either helium (He) or argon (Ar). The particle surface becomes carbon-rich with carbon monoxide (CO) / He plasmas. By immersing the plasma-treated n-Al in an iodic acid (HIO3) solution, AIH crystals can be formed on the n-Al surface. Transmission electron microscopy (TEM) is used as a major tool to study the details of the modified surface morphologies, diffraction patterns, and chemical composition of the modified n-Al. The results demonstrate effective surface passivation of n-Al via atmospheric plasma techniques.

In this paper, a novel NiFe-LDH@ZnO composite was prepared by using a facile two-step process upon nickel foam (NF) substrate. The morphologies and chemical compositions of the samples were characterized by SEM, EDS, XRD and XPS. Photocatalytic degradation of Rhodamine B dye was tested with the samples NiFe-LDH@ZnO@NF, ZnO@NF and NiFe-LDH under the same conditions. The experimental results revealed that the NiFe-LDH@ZnO@NF composite exhibited excellent photocatalytic performance, i.e., 1.4 and 2.5 times higher than that of pure ZnO and NiFe-LDH, respectively. The reason was that the NiFe-LDH@ZnO@NF composite provided a possibility to effectively inhibit the recombination of the photogenerated electron-hole pairs, and therefore enhanced the photocatalytic efficiency. This composite is expected to have potential applications in wastewater treatment field.

We report evolution of the surface and wetting behavior of Barium fluoride (BaF2) thin films under the effect of swift heavy ion (SHI) irradiation at different fluences. The analogy of this study may be used may be used for the development of dust resistant fabric technology for rural area. The ion irradiation has been performed at normal incidence on the films with Au ions having 100 MeV energy. Further, the wettability of irradiated surfaces is studied through contact angle of water droplet. The value of contact angle of droplet changes with irradiation, it increases from 111° to 123° with the increase in fluence from 5×1011 to 1×1013 ions/cm2. The mechanism of wettability of BaF2 is explained on the basis of increase in contact area of water droplet with surface. SHI irradiation deposits a huge amount of energy in materials due to extreme electronic excitation and it causes a large increase in the temperature of material around the ion track. Ion beam irradiation leads to the large ejection of atoms from the surface which is one of the major factors in increasing the roughness of the surface and thus for the change in contact angle.

In order to understand the impact of nano-crystallites on current transport mechanisms in screen-printed c-Si solar cells with lowly-doped emitter, Te-glass based Ag pastes with different transition temperatures (Tg) were used. The Te-glass with lower Tg showed lower Rc than the one with higher Tg due to the formation of nano-crystallites in the glass layer. These nano-crystallites enhance the conductivity of the glass and lead to higher fill factor (FF). The nature of these nano-crystallites was first identified by the Raman spectrometry and the peaks at 76 cm-1, 119 cm-1 and 145 cm-1 were corresponding to Ag2Te and PbTe. The conductive-AFM further confirmed the high conductivity of these nano-crystallites without pyramidal Ag crystallites, which means the current transporting from Si emitter to Ag gridlines is mainly through the nano-crystallites in the glass.

We use irradiation with 50-MeV Cu-ions to create vortex pinning defects in high-temperature superconducting Y1Ba2Cu3O7-x coated conductors using a beam-rastering approach that allows for the uniform irradiation of large ample areas. Our samples contain barium zirconate nanorods as pre-existing vortex pinning defects. By irradiating the samples at angles of 0o, 15oand 30o from the crystallographic c-axis we explore the interplay between pre-existing and irradiation-induced pinning and find that irradiation at 30o leads to a moderate enhancement of Jc at 5 K at high fields (greater than 2 Tesla). In contrast, Jc was suppressed for all temperatures and fields for other angles of irradiation. Optimized particle irradiation procedures offer a way for improving the performance of high-temperature superconducting wires for use in high magnetic fields without the need for changing wire synthesis protocols.

This work presents the synthesis and characterization of a pearylated polysiloxane material (PAP) from a polycondensation reaction, followed by functionalization with HClSO3 by an electrophilic substitution reaction. According to the characterization techniques applied, a sulfonated pearylated polysiloxane was also obtained, (SPAP). The purpose of this sulfonated material is to obtain an ionomer able to be applied in hydrogen fuel cells of the proton exchange membrane kind (PEMFC). The reaction to produce the polysiloxane precursor was carried out with the commercial reagents: PhSiCl3, Ph2SiCl2 and Ph3SiCl in anhydrous THF at 75 °C and the SPAP material was obtained by sulfonation of the precursor with chlorosulfonic acid. PAP and SPAP were characterized by 1H, NMR for liquids, 29Si NMR for solids, IR-ATR, SEM, and cyclic voltammetry. The NMR 29Si spectra show that PAP and PAPS contain crosslinking regions due to PhSiCl3, growing chain zones due to Ph2SiCl2 and polymer termination zones due to Ph3SiCl, obtaining a mixture of siloxanes. The analysis by cyclic voltammetry indicates that by integrating the area under the curve of the adsorption peaks of H2, a value of 0.062 mC/cm2 is obtained, a value close to the commercial ionomer of Nafion®.

Phonons are critical in understanding the electronic, optical and optoelectronic properties of transition metal dichalcogenides (TMDs). The interpretation of lineshapes is important for understanding the effect of specific physical processes on the electronic, optical and optoelectronic properties of TMDs. We employ an analytical approach to investigate the influence of the layered effect, the quantum size effect, the Breit-Wigner-Fano effect, and the inhomogeneous heating effect on the phonon lineshape of TMDs, using WS2 and MoS2 as prototypes. We demonstrate the similarities and differences in how individual processes affect the lineshapes and also the effect of combining processes. Such an approach is useful in guiding the interpretation of the phonon lineshapes of TMDs in particular, and nanostructures in general.