25th Anniversary Article: Exploring Nanoscaled Matter from Speciation to Phase Diagrams: Metal Phosphide Nanoparticles as a Case of Study

The notions of nanoscale “phase speciation” and “phase diagram” are defined and discussed in terms of kinetic and thermodynamic controls, based on the case of metal phosphide nanoparticles. After an overview of the most successful synthetic routes for these exotic nanomaterials, the cases of InP, Ni₂P, Ni₁₂P₅ and Pd_xP_y are discussed in detail to highlight the relationship between composition, structure, and size at the nanoscale. The influence of morphology is discussed next by comparing the behavior of Cu₃P nanophases with those of Ni_xP_y, FeP/Fe₂P, and CoP/Co₂P. Perspectives provide the reader with methodological guidelines for further investigation of nanoscale “phase diagrams”, and their use for optimized synthesis of new functional nanomaterials.     

Understanding barriers to home‐based and self‐care in‐center hemodialysis

Despite superior outcomes and lower associated costs, relatively few patients with end‐stage renal disease undergo self‐care or home hemodialysis. Few studies have examined patient‐ and physician‐specific barriers to self‐care and home hemodialysis in the modern era. The degree to which innovative technology might facilitate the adoption of these modalities is unknown. We surveyed 250 patients receiving in‐center hemodialysis and 51 board‐certified nephrologists to identify key barriers to adoption of self‐care and home hemodialysis. Overall, 172 (69%) patients reported that they were “likely” or “very likely” to consider self‐care hemodialysis if they were properly trained on a new hemodialysis system designed for self‐care or home use. Nephrologists believed that patients were capable of performing many dialysis‐relevant tasks, including: weighing themselves (98%), wiping down the chair and machine (84%), clearing alarms during treatment (53%), taking vital signs (46%), and cannulating vascular access (41%), but thought that patients would be willing to do the same in only 69%, 34%, 31%, 29%, and 16%, respectively. Reasons that nephrologists believe patients are hesitant to pursue self‐care or home hemodialysis do not correspond in parallel or by priority to reasons reported by patients. Self‐care and home hemodialysis offer several advantages to patients and dialysis providers. Overcoming real and perceived barriers with new technology, education and coordinated care will be required for these modalities to gain traction in the coming years.     

Focused Ultrasound Preconditioning for Augmented Nanoparticle Penetration and Efficacy in the Central Nervous System

Microbubble activation with focused ultrasound (FUS) facilitates the noninvasive and spatially‐targeted delivery of systemically administered therapeutics across the blood–brain barrier (BBB). FUS also augments the penetration of nanoscale therapeutics through brain tissue; however, this secondary effect has not been leveraged. Here, 1 MHz FUS sequences that increase the volume of transfected brain tissue after convection‐enhanced delivery of gene‐vector “brain‐penetrating” nanoparticles were first identified. Next, FUS preconditioning is applied prior to trans‐BBB nanoparticle delivery, yielding up to a fivefold increase in subsequent transgene expression. Magnetic resonance imaging (MRI) analyses of tissue temperature and K_trans confirm that augmented transfection occurs through modulation of parenchymal tissue with FUS. FUS preconditioning represents a simple and effective strategy for markedly improving the efficacy of gene vector nanoparticles in the central nervous system.     

Molecular Switch Controlled by Pulsed Bias Voltages

Recent experiments have shown that the current–voltage characteristics (I–V) of BPDN‐DT (bipyridyl‐dinitro oligophenylene‐ethynylene dithiol) can be switched in a very controlled manner between “on” and “off” traces by applying a pulse in a bias voltage, V_bias. Here, the polaron formation energies are calculated to check a frequently held belief, namely, that the polaron formation can explain the observed bistability. These results are not consistent with such a mechanism. Instead, a conformational reorientation is proposed. The molecule carries an intrinsic dipole moment, which couples to V_bias. Ramping V_bias exerts a force on the dipole that can reorient (“rotate”) the molecule from the ground state (“off”) into a metastable configuration (“on”) and back. By elaborated electronic structure calculations, a specific path for this rotation is identified through the molecule's conformational phase space. It is shown that this path has sufficiently high barriers to inhibit thermal instability but that the molecule can still be switched in the voltage range of the junction stability. The theoretical I–Vs qualitatively reproduce the key experimental observations. A proposal for the experimental verification of the alternative mechanism of conductance switching is presented.     

Tunable Photocontrolled Motions Using Stored Strain Energy in Malleable Azobenzene Liquid Crystalline Polymer Actuators

A new strategy for enhancing the photoinduced mechanical force is demonstrated using a reprocessable azobenzene‐containing liquid crystalline network (LCN). The basic idea is to store mechanical strain energy in the polymer beforehand so that UV light can then be used to generate a mechanical force not only from the direct light to mechanical energy conversion upon the trans–cis photoisomerization of azobenzene mesogens but also from the light‐triggered release of the prestored strain energy. It is shown that the two mechanisms can add up to result in unprecedented photoindued mechanical force. Together with the malleability of the polymer stemming from the use of dynamic covalent bonds for chain crosslinking, large‐size polymer photoactuators in the form of wheels or spring‐like “motors” can be constructed, and, by adjusting the amount of prestored strain energy in the polymer, a variety of robust, light‐driven motions with tunable rolling or moving direction and speed can be achieved. The approach of prestoring a controllable amount of strain energy to obtain a strong and tunable photoinduced mechanical force in azobenzene LCN can be further explored for applications of light‐driven polymer actuators.     

Analysis of the First Ten Years of the Journal of Engineering Education

The analysis of the Journal of Engineering Education (JEE) is extended to the ten year period from 1993 through 2002. The most common keywords remain teaching, computers and design although “assessment” and “ABET” became popular from 1998 to 2002. The most cited reference and author are ABET Criterion 2000 and Richard Felder, respectively. The median number of JEE citations of articles published in JEE during 1993 and 1994 is one. The number of papers with financial support increased by over 80 percent. NSF is the dominant source of support. Comparing the second five‐year period to the first five‐year period, there were increases in the percentages of papers reporting data, doing assessment, and using educational or learning theories. These results are consistent with a journal that is becoming more research oriented.     

Breathable Nanowood Biofilms as Guiding Layer for Green On‐Skin Electronics

Thin‐film electronics are urged to be directly laminated onto human skin for reliable, sensitive biosensing together with feedback transdermal therapy, their self‐power supply using the thermoelectric and moisture‐induced‐electric effects also has gained great attention (skin and on‐skin electronics (On‐skinE) themselves are energy storehouses). However, “thin‐film” On‐skinE 1) cannot install “bulky” heatsinks or sweat transport channels, but the output power of thermoelectric generator and moisture‐induced‐electric generator relies on the temperature difference (?T ) across generator and the ambient humidity (AH), respectively; 2) lack a routing and accumulation of sweat for biosensing, lack targeted delivery of drugs for precise transdermal therapy; and 3) need insulation between the heat‐generating unit and heat‐sensitive unit. Here, two breathable nanowood biofilms are demonstrated, which can help insulate between units and guide the heat and sweat to another in‐plane direction. The transparent biofilms achieve record‐high transport_///transport_⊥ (//: along cellulose nanofiber alignment direction, ⊥: perpendicular direction) of heat (925%) and sweat (338%), winning applications emphasizing on ?T/AH‐dependent output power and “reliable” biosensing. The porous biofilms are competent in applications where “sensitive” biosensing (transporting_// sweat up to 11.25 mm s^?1 at the 1st second), “insulating” between units, and “targeted” delivery of saline‐soluble drugs are of uppermost priority.     

EBSD Study of Microstructural Evolution in a Nickel‐Base Superalloy during Two‐Pass Hot Compressive Deformation

Generally, the high‐temperature deformation characteristics and microstructural evolution of alloys are studied by isothermal compressive experiments at stable strain rates. But, the strain rate is variant during the practice industrial production of components. In this work, isothermal two‐pass hot compression experiments with stepped strain rates are performed to analyze the microstructural evolution of a nickel‐base superalloy with δ phase. Results reveal that the mean grain size decreases, but the percentage of undissolved δ phases increases, as the strain rate of the first pass (SROFP) is increased. However, the mean grain size and the percentage of undissolved δ phases decreases with the increase of inter‐pass time (IPT) or the true strain of the first pass (TSOFP). Meanwhile, the increased deformation temperature easily enlarges the mean grain size, but obviously decreases the percentage of undissolved δ phases. In addition, the evolution of Σ3ⁿ boundaries not only results from the “new twinning mechanism”, but also “Σ3ⁿ regeneration mechanism”. “Σ3ⁿ regeneration mechanism” becomes predominant with decreasing SROFP or increasing IPT/TSOFP. Besides, “new twinning mechanism” plays a major role on Σ3ⁿ boundaries evolution as the temperature is increased from 950 to 980 °C, and then become weaken with further increasing the deformation temperature.

     

Optically Rewritable Transparent Liquid Crystal Displays Enabled by Light‐Driven Chiral Fluorescent Molecular Switches

Functional soft materials exhibiting distinct functionalities in response to a specific stimulus are highly desirable towards the fabrication of advanced devices with superior dynamic performances. Herein, two novel light‐driven chiral fluorescent molecular switches have been designed and synthesized that are able to exhibit unprecedented reversible Z/E photoisomerization behavior along with tunable fluorescence intensity in both isotropic and anisotropic media. Cholesteric liquid crystals fabricated using these new fluorescent molecular switches as chiral dopants exhibit reversible reflection color tuning spanning the visible and infrared region of the spectrum. Transparent display devices have been fabricated using both low chirality and high chirality cholesteric films that operate either exclusively in fluorescent mode or in both fluorescent and reflection mode, respectively. The dual mode display device employing short pitch cholesteric film is able to function on demand under all ambient light conditions including daylight and darkness with fast response and high resolution. Moreover, the proof‐of‐concept for a “remote‐writing board” using cholesteric films containing one of the light‐driven chiral fluorescent molecular switches with ease of fabrication and operation is disclosed herein. Such optically rewritable transparent display devices enabled by light‐driven chiral fluorescent molecular switches pave a new way for developing novel display technology under different lighting conditions.     

Angular-Independent Photonic Pigments via the Controlled Micellization of Amphiphilic Bottlebrush Block Copolymers

Photonic materials with angular-independent structural color are highly desirable because they offer the broad viewing angles required for application as colorants in paints, cosmetics, textiles, or displays. However, they are challenging to fabricate as they require isotropic nanoscale architectures with only short-range correlation. Here, porous microparticles with such a structure are produced in a single, scalable step from an amphiphilic bottlebrush block copolymer. This is achieved by exploiting a novel “controlled micellization” self-assembly mechanism within an emulsified toluene-in-water droplet. By restricting water permeation through the droplet interface, the size of the pores can be precisely addressed, resulting in structurally colored pigments. Furthermore, the reflected color can be tuned to reflect across the full visible spectrum using only a single polymer (M_n = 290 kDa) by altering the initial emulsification conditions. Such “photonic pigments” have several key advantages over their crystalline analogues, as they provide isotropic structural coloration that suppresses iridescence and improves color purity without the need for either refractive index matching or the inclusion of a broadband absorber.     

Analyzing Behavioral Big Data: Methodological,practical, ethical,and moral issues

ABSTRACT

The term “big data” evokes emotions ranging from excitement to exasperation in the statistics community. Looking beyond these emotions reveals several important changes that affect us as statisticians and as humans. I focus on Behavioral Big Data (BBD), or very large and rich multidimensional datasets on human behaviors, actions, and interactions, which have become available to companies, governments, and researchers. This article describes the BBD landscape and examines opportunities and critical issues that arise when applying statistical and data mining approaches to Behavioral Big Data, including the move from macro- to micro-decisioning and its implications.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Biomimetic Pathways for Nanostructured Poly(KAMPS)/aragonite Composites that Mimic Seashell Nacre

Complex microstructures of biominerals such as seashell nacre, bone, and teeth are awe‐inspiring. Nature has devised schemes to combine hard inorganic platelets of aragonite (CaCO₃) and an organic matrix that produce tough biocomposites. The ability of the organic‐inorganic components to “slide” internally leads to the toughening of the materials, though a recreation of this system at the nanoscale has yet to be shown. Here, we implement a poly(KAMPS)‐based assembly, which is carried out entirely from dilute aqueous solutions of the materials to create a “brick and mortar”‐type aragonite structure that mimics the platelet sliding and exhibits toughening. The negatively charged poly(KAMPS) chains are attracted to the positively charged divalent cations, by which addition of NaHCO₃ to an aqueous mixture of Ca²⁺‐poly(KAMPS), results in the growth of aragonite nanorods with a width of 120 nm. The reversible nature of the physical gel formation of poly(KAMPS) in solution results in adhesion of the nanorods into a microscale structure. The new nacre‐like carbonate composite, has a modulus (44 GPa) and hardness (2.8 GPa) on a similar order as to that of nacre and other bio‐composites, exhibits limited creep, and demonstrates a mechanism with nanoscale deformation.     

Determination of local characteristics for the application of the Weakest‐Link Model

The Weakest‐Link model is based on defects that are statistically distributed within the material with local stress. The failure at least at one defect causes the failure of the total structure. Based on this model, the so‐called statistic size effect can be evaluated in the case of cyclic loading and in the case of static loading the failure behaviour of ferritic steel within the brittle fracture range is highlighted. The application of the Weakest‐Link model requires the allocation of the local characteristics ‐ surface and / or volume ‐ to the discrete points of the stress. By using the method “SPIEL” which is independent from the FE code used, the allocation of couples of values ‐surface and stress and / or volume and stress ‐ by a suitable choice of unit load cases is possible. In consequence of the method “SPIEL” particularities are to be taken into consideration. In the present paper these particularities will be described exemplarily for the FE programs ABAQUS¹ and ANSYS².     

Large “Pillow” Fullerenes Hydrogenated at the Inter‐sheet “Seam”

Abstract

In a previous paper on large “pillow” fullerenes, various systems were described with 12 pentagons connecting 2 parallel hexagonal arrays of benzenoid rings (graphene fragments functioning as the faces of the “pillow”) on top of each other. Additional bonds between these identical arrays formed only from sp²‐hybridized carbon atoms gave rise to hexagons and 12 pentagons along the “seam” or “rim.” High steric strain was associated with curvature around the pentagons due to connections between the 2 pillow faces involving bonds between 2 sp²‐hybridized carbon atoms. The present paper examines similar “quasi‐graphitic” structures in which some carbon atoms of the rim between the two raphene faces have hydrogen atoms attached to them, i.e., have sp³‐hybridization, alleviating thereby some strain.     

Engineering Entrepreneurship: An Example of A Paradigm Shift in Engineering Education

This paper describes a course on technology‐based entrepreneurship. Brown University's Division of Engineering has created a two‐semester course sequence designed to introduce students to entrepreneurship through a unique merger of classroom learning and industry participation. The course is open to advanced undergraduates from all engineering disciplines, and emphasis is placed upon recruiting almost half of the student participants from outside of engineering in order to develop “team building” skills. Local “parent companies” provide seed ideas or concepts to student groups who use skills learned in the classroom (both in this course as well as other courses) to develop and refine the parent company's idea and turn it into a viable simulated spin‐off business or new start‐up. Managers from the parent companies serve in an evolving role over the two‐semester sequence beginning as a “board of directors” for the spin‐off and eventually evolving into a potential source of start‐up capital (or possibly a customer for the products of the company). The faculty carefully manage the student‐company interface. Deliverables at the end of the two‐semester sequence include a business plan and a prototype product.     

Thermally Driven Transport and Relaxation Switching Self‐Powered Electromagnetic Energy Conversion

Electromagnetic energy radiation is becoming a “health‐killer” of living bodies, especially around industrial transformer substation and electricity pylon. Harvesting, converting, and storing waste energy for recycling are considered the ideal ways to control electromagnetic radiation. However, heat‐generation and temperature‐rising with performance degradation remain big problems. Herein, graphene‐silica xerogel is dissected hierarchically from functions to “genes,” thermally driven relaxation and charge transport, experimentally and theoretically, demonstrating a competitive synergy on energy conversion. A generic approach of “material genes sequencing” is proposed, tactfully transforming the negative effects of heat energy to superiority for switching self‐powered and self‐circulated electromagnetic devices, beneficial for waste energy harvesting, conversion, and storage. Graphene networks with “well‐sequencing genes” (w = P_c/P_p > 0.2) can serve as nanogenerators, thermally promoting electromagnetic wave absorption by 250%, with broadened bandwidth covering the whole investigated frequency. This finding of nonionic energy conversion opens up an unexpected horizon for converting, storing, and reusing waste electromagnetic energy, providing the most promising way for governing electromagnetic pollution with self‐powered and self‐circulated electromagnetic devices.     

Moving Droplets in 3D Using Light

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical “fuel,” a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s^?1 toward or away from the irradiation source as a result of a light‐induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a “cargo” and moving the new larger droplet to a “reactor” droplet where the cargo undergoes a chemical reaction. The control and versatility of this light‐activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.     

Liquid‐Crystalline Dynamic Networks Doped with Gold Nanorods Showing Enhanced Photocontrol of Actuation

A near‐infrared‐light (NIR)‐ and UV‐light‐responsive polymer nanocomposite is synthesized by doping polymer‐grafted gold nanorods into azobenzene liquid‐crystalline dynamic networks (AuNR‐ALCNs). The effects of the two different photoresponsive mechanisms, i.e., the photochemical reaction of azobenzene and the photothermal effect from the surface plasmon resonance of the AuNRs, are investigated by monitoring both the NIR‐ and UV‐light‐induced contraction forces of the oriented AuNR‐ALCNs. By taking advantage of the material's easy processability, bilayer‐structured actuators can be fabricated to display photocontrollable bending/unbending directions, as well as localized actuations through programmed alignment of azobenzene mesogens in selected regions. Versatile and complex motions enabled by the enhanced photocontrol of actuation are demonstrated, including plastic “athletes” that can execute light‐controlled push‐ups or sit‐ups, and a light‐driven caterpillar‐inspired walker that can crawl forward on a ratcheted substrate at a speed of about 13 mm min^‐1. Moreover, the photomechanical effects arising from the two types of light‐triggered molecular motion, i.e., the trans–cis photoisomerization and a liquid‐crystalline–isotropic phase transition of the azobenzene mesogens, are added up to design a polymer “crane” that is capable of performing light‐controlled, robot‐like, concerted macroscopic motions including grasping, lifting up, lowering down, and releasing an object.     

The UIUC Virtual Spectrometer: A Java‐Based Collaborative Learning Environment

The development of the UIUC Virtual Spectrometer (UIUC‐VS), an interactive, Java‐based simulation and tutoring system, is discussed. The apprenticeship model of learning is utilized to create a learning environment for the study of a one‐dimensional proton nuclear magnetic resonance (NMR) experiment, with the goal of linking theoretical knowledge with practical operational experience. Active, exploratory, apprentice‐style learning is supported via modes of operation within the system. Students can flexibly choose to “observe the expert” perform and explain operational steps, or “act as an apprentice” and carry out the steps autonomously. Students can switch between modes at their discretion, giving them control of the level of system intervention. Students can also explore and reflect on an “information space” of objects, procedures, and related concepts. UIUC‐VS extends a previous tutorial application, LEMRS,¹ using Java‐based, Web‐capable technologies to provide a basis for a shared simulation environment teaching NMR. As a computer‐supported collaborative learning environment, the system includes a method of asynchronous communication, where the student can post questions and comments to a “question board,” with the ability to capture the current state of the system via annotations on a screen capture. Formative evaluations involving undergraduate chemistry students were crucial to system redesign.