Mediated Electrochemistry to Mimic Biology's Oxidative Assembly of Functional Matrices

Biology uses diffusible oxidants to perform functions that range from signaling to matrix assembly, and these oxidation chemistries offer surprising selectivities. Here, it is reported that mediated electrochemistry can access the richness of such oxidation chemistries. Specifically, electrode‐imposed voltage inputs are used to locally generate oxidized mediators that can diffuse into polymer solutions and induce the formation of covalent bonds for the deposition and functionalization of hydrogels at the electrode surface. Depending on the mediator's redox potential (E⁰), it is possible to “gate” the voltage inputs to target specific residues (e.g., thiols or amines) and oxidation chemistries. Further, mediators of varying E⁰ offer different reactivities and thus allow control of reaction‐diffusion rates to modulate the hydrogel's crosslink density and mechanical properties. Importantly, this mediated oxidation can be performed under physiologically relevant conditions to preserve labile biological functionalities (e.g., cell viability and protein function). Finally, it is demonstrated that protein fusion tags can be engineered to have “targetable” amino acid residues that enable protein function to be oxidatively conjugated to electrodeposited hydrogels. In summary, mediated electrochemistry can engage orthogonal oxidation chemistries to create functionalized matrices and thus mediated electrochemistry should add important capabilities to the electrofabrication toolbox.     

A digitally temperature-compensated crystal oscillator

The base frequency of oscillators used in the Global System for Mobile Communication (GSM) network or Global Positioning System (GPS) receiver applications needs to be very stable with respect to temperature and supply-voltage variations. One approach to obtain extremely good frequency stability is the use of oven-stabilized crystal oscillators. With this kind of oscillator, a frequency stability versus temperature of a few ppb versus the standard temperature range can be achieved. In this paper, a digitally compensated crystal oscillator is described. The system provides a frequency stability of (Δf)/f<1.5 ppm for a temperature range of -40°C to 90°C compared to about ±20 ppm for a noncompensated crystal. The core of the system is an application-specified integrated circuit (ASIC) fabricated in a standard 0.8-μm CMOS process. The power consumption for the oscillator running at 13 MHz is 100 mW. The final device equipped with the ASIC, crystal blank, and a few external components fits into a 14×9×3 mm³ package     

77 GHz soliton modelocked Nd:YVO4 laser

An Nd:YVO₄ laser which was passively modelocked at the very high repetition rate of ~77 GHz, using a semiconductor saturable absorber mirror (SESAM), is demonstrated. The soliton-like pulses are well separated in time and their duration is 2.7 ps. The required negative dispersion is introduced by a GTI-like structure, which is formed by the gain medium and the SESAM     

Elucidating the challenges for the praxis of fog computing: An aspect‐based study

The evolutionary advancements in the field of technology have led to the instigation of cloud computing. The Internet of Things paradigm stimulated the extensive use of sensors distributed across the network edges. The cloud datacenters are assigned the responsibility for processing the collected sensor data. Recently, fog computing was conceptuated as a solution for the overwhelmed narrow bandwidth. The fog acts as a complementary layer that interplays with the cloud and edge computing layers, for processing the data streams. The fog paradigm, as any distributed paradigm, has its set of inherent challenges. The fog environment necessitates the development of management platforms that effectuates the orchestration of fog entities. Owing to the plenitude of research efforts directed toward these issues in a relatively young field, there is a need to organize the different research works. In this study, we provide a compendious review of the research approaches in the domain, with special emphasis on the approaches for orchestration and propose a multilevel taxonomy to classify the existing research. The study also highlights the application realms of fog computing and delineates the open research challenges in the domain.     

Enhanced Osteoblast Adhesion to Epoxide‐Functionalized Surfaces

As an alternative to expensive extracellular matrix (ECM) proteins generally applied as coatings in Petri dishes used for cell binding, an innovative system based on epoxide‐functionalized monolayers capable of protein binding is proposed. Since cells bind to material surfaces through proteins, protein‐binding surfaces should also promote cell binding. Here we investigate how the cell‐binding properties of an epoxide‐functionalized surface compares with ECM protein gel coated surfaces and tissue culture polystyrene control surfaces. Glass surfaces are functionalized with glycidoxypropyltriethoxysilane (GOPS), which results in an epoxide‐functionalized surface capable of binding proteins through an epoxide–amine reaction. Advancing contact angle measurements and atomic force microscopy measurements confirm the formation of a homogeneous GOPS monolayer. This monolayer is micropatterned with fluorescein‐labeled ECM protein gel by microcontact printing (µCP). Confocal laser scanning microscopy (CLSM) shows accurately transferred ECM protein gel micropatterns. Osteoblasts that are seeded on these micropatterned substrates show a clear preference for adhering to the epoxide‐functionalized areas. The morphology of these cultured osteoblasts is needle‐like with high aspect ratios. As controls, osteoblasts are cultured on GOPS‐functionalized surfaces, unstructured ECM protein gel surfaces, and tissue culture polystyrene (TCPS). The GOPS surfaces demonstrate a drastic increase in cell adhesion after 2 h, whilst the other tests show no adverse effects of this surface on the osteoblasts as compared to ECM and TCPS. CLSM shows healthy cell morphologies on each surface. It is demonstrated for the first time that epoxide groups outperform ECM protein gel in cell adhesion, thereby providing new routes for cost‐effective coatings that improve biocompatibility as well as exciting, new methodologies to control and direct cell adhesion.     

3D printing as a means of learning and communication: The 3Ducation project revisited

This research project explores to what extent the utilization of open-source 3D printers and 3D design software could serve as means of learning and communication. The principles of non-formal education aligned with the concept of constructionism are used to create an experimental educational scenario focused on geocultural tourism for persons with visual impairments. This paper documents our experience and presents our findings from a 25-day long project, which took place in Zagori, northwestern Greece. 11 high school students from Portugal designed and manufactured natural and cultural heritage artifacts carrying messages in the Braille language. The objects were then handed to people with visual impairments with a twofold aim. First, to enable the communication among persons with and without visual impairments; and, second, to empower students to participate in training projects through open educational procedures. We conclude that open educational practices can boost students’ active engagement in educational processes. Finally, 3D printing encourages a meaningful communication among people with and without visual impairments via the tangible exploration of geocultural components.     

A Novel Buffering Technique for Aqueous Processing of Zinc Oxide Nanostructures and Interfaces,and Corresponding Improvement of Electrodeposited ZnO‐Cu2O Photovoltaics

A novel buffering method is presented to improve the stability of zinc oxide processed in aqueous solutions. By buffering the aqueous solution with a suitable quantity of sacrificial zinc species, the dissolution of functional zinc oxide structures and the formation of unwanted impurities can be prevented. The method is demonstrated for ZnO films and nanowires processed in aqueous solutions used for the selective etching of mesoporous anodic alumina templates and the electrochemical deposition of Cu₂O. In both cases, improved ZnO stability is observed with the buffering method. ZnO‐Cu₂O heterojunction solar cells (bilayer and nanowire cells) synthesized using both traditional and buffered deposition methods are characterized by impedance spectroscopy and solar simulation measurements. Buffering the Cu₂O deposition solution is found to reduce unwanted recombination at the heterojunction and improve the photovoltaic performance.     

Reaction chemistry and resulting surface structure of HgCdTe etched in CH4/H2 and H2 ECR plasmas

We report on several new aspects of etching of Hg_1−xCd_xTe (x = 0.22), HgTe, and CdTe in CH₄/H₂/Ar plasmas generated by an electron cyclotron resonance plasma source. Using a residual gas analyzer, we have identified elemental Hg, TeH₂, Te(CH₃)₂, and Cd(CH₃)₂ as the primary reaction products escaping from a HgCdTe surface during the plasma exposure. We have also demonstrated that a bias is not needed to etch HgCdTe at moderate temperatures (30-40°C), as previously suggested by other researchers. We have also developed a technique that avoids the formation of hydrocarbon polymer films on a HgCdTe sample during etching. Moreover, we have examined by x-ray photoelectron spectroscopy analysis and ellipsometry the surface condition of HgCdTe resulting from etching with this technique at zero bias. After exposure to the CH₄/H₂Ar plasma (or to a H₂/Ar plasma only), the HgCdTe samples exhibited a depletion of the HgTe component in the near surface region (increase of the x-value). The depletion covered a range from virtually x = 1 after H₂/Ar (10:2 in sccm) etching to values 0.4 < x < 0.5 after CH₄/H₂Ar (7:7:2 in seem) etching. Exposures to the plasmas were found to result in surface roughening of HgCdTe, however, plasmas rich in H₂ were observed to cause significantly rougher surfaces than plasmas with small H₂/CH₄ ratios. This difference in the resulting surface condition is attributed solely to chemical effects since the respective ion energies are considered to be below the damage threshold for HgCdTe in both cases. We also investigated the etching of HgTe and CdTe single crystals. The etch rate of HgTe was found to be over one order of magnitude higher than that of CdTe under similar conditions. This large difference in etch rates is assumed to be responsible for the observed preferential etching of the HgTe component indicated by the HgTe depletion of the HgCdTe surface region.     

Layer‐by‐Layer All‐Inorganic Quantum‐Dot‐Based LEDs: A Simple Procedure with Robust Performance

A novel all‐inorganic electroluminescent device is demonstrated based on highly luminescent CdTe nanocrystals intercalated within a laminar hydrotalcite‐like structure. The laminar scaffold acts to both support and distribute the CdTe nanocrystals. The device is synthesized using simple wet chemical processes at room temperature in ambient conditions. It has high thermal stability, operating continuously up to 90 °C, and a maximum efficiency at J = 0.12 A cm^?2. The device is targeted at the automotive industry.     

A Direct Approach to Organic/Inorganic Semiconductor Hybrid Particles via Functionalized Polyfluorene Ligands

Controlled Suzuki–Miyaura coupling polymerization of 7′‐bromo‐9′,9′‐dioctyl‐fluoren‐2′‐yl‐4,4,5,5‐tetramethyl‐[1,3,2]dioxaborolane initiated by bromo(4‐tert‐butoxycarbonylamino‐phenyl)(tri‐tert‐butylphosphine)palladium ( 1 ) or bromo(4‐diethoxyphosphoryl‐phenyl)(tri‐tert‐butylphosphine)palladium ( 2 ) yields functionalized polyfluorenes (M_n = 4 × 10³ g mol^?1, M_w/M_n < 1.2) with a single amine or phosphonic acid, respectively, end‐group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino‐functionalized polyfluorene ligands. Single particle micro‐photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.