bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elemental 2D Materials: Solution‐Processed Synthesis and Applications in Electrochemical Ammonia Production
Authors: Bat‐Erdene Munkhjargal , Bati Abdulaziz S. R. , Qin Jiadong , Zhao Huijun , Zhong Yu Lin , Shapter Joseph G. , Batmunkh Munkhbayar 
Published: October 2021

AbstractGraphene and related elemental 2D materials have become core materials in nanotechnology and shown great promise for industrially important electrocatalysis reactions. Although excellent progress has been made over the past few years, research into the field of elemental 2D materials beyond graphene is still at an early stage. Importantly, recent research has revealed the promising efficacy of elemental 2D materials as effective nitrogen reduction reaction (NRR) electrocatalysts due to their many excellent properties including high surface activities, acting as active sites for effective functionalization and defect engineering. This review provides a comprehensive account of recent advances in elemental 2D materials with a major focus on the solution‐based synthesis routes and their applications in electrocatalytic NRR for ammonia (NH3) production. After a concise overview of elemental 2D materials, the advantages and challenges of currently available methods for the synthesis of these 2D materials are discussed. Then, the review focuses on the use of these emerging 2D materials in the electrocatalytic reduction of N2 for sustainable (NH3) synthesis. Finally, the challenges still to be addressed, and important perspectives in this attractive field are emphasized.
The Impact of Ion Migration on the Electro‐Optic Effect in Hybrid Organic–Inorganic Perovskites
Authors: Sun Meng‐Jia , Sabatini Randy , Wang Pei‐Xi , Najarian Amin Morteza , Bertens Koen , Johnston Andrew , Hoogland Sjoerd , Sargent Edward H. 
Published: October 2021

AbstractElectro‐optic (EO) modulation allows the conversion of electrical signals to optical pulses and is widely employed in telecommunications and chip‐to‐chip interconnects. Recently, hybrid organic–inorganic perovskites (HOIPs) have been explored as candidates for EO modulators. To improve the EO performance, it is envisioned that halide doping will lower the symmetry of the crystal, enhancing spontaneous polarization. However, mixed halide perovskites are often associated with ion migration, which may impact their EO properties. Thus, the influence of ion migration on the EO efficiency is investigated using Br‐doped Dion–Jacobson quasi‐2D HOIPs, (4AMP)(MA)Pb2(Brx/I1−x)7 (4AMP = 4‐(aminomethyl)piperidinium, MA = methylammonium). While density functional theory predicts a greater spontaneous polarization for the Br‐doped sample, it is found that experimental results are affected by ion migration. The EO coefficient of the Br/I mixed sample is 95 pm V−1 at 1 kHz (≈50× higher than the undoped sample), but the response falls off rapidly with frequency. This frequency dependence is correlated with impedance spectroscopy, showing that the large EO signal results from ion migration. This study shows that ion migration impacts the EO analysis of mixed halide perovskites and must be considered in future EO studies.
Targeted Therapeutics Delivery by Exploiting Biophysical Properties of Senescent Cells
Authors: Low Jessalyn , Chan Brian , Tay Andy 
Published: October 2021

AbstractCellular senescence refers to a state of irreversible arrest of cell proliferation in response to various forms of cellular stress. It is known that the accumulation of senescent cells is a hallmark of aging, and mounting evidence has shown that the chronic accumulation of senescent cells is a significant contributor to various deleterious age‐related pathologies. To limit the detrimental impacts of cellular senescence, there has been growing interest in targeted delivery of therapeutics to senescent cells to treat age‐related pathologies and promote healthy aging. Two popular strategies include the elimination of senescent cells using senolytic drugs, and rejuvenation of senescent cells. To that end, it is integral that the delivery of senolytics, senomorphics or rejuvenating biomolecules to senescent cells are highly selective to enhance delivery efficacy and safety. However, there is little understanding of how senescence‐associated biophysical changes such as cellular size and stiffness can be exploited for targeted therapeutics delivery. In this review, the biomolecular and biophysical markers of senescence along with senescence models and emerging therapeutics are first described. This review then focuses on how biophysical properties can be exploited for targeted therapeutics delivery, using approaches like nanoparticles, electroporation, sonoporation, photoporation and high aspect‐ratio nanostructures to senescent cells.
Hydroquinone versus Pyrocatechol Pendants Twisted Conjugated Polymer Cathodes for High‐Performance and Robust Aqueous Zinc‐Ion Batteries
Authors: Wang Xinlei , Xiao Jijun , Tang Weihua 
Published: October 2021

AbstractAqueous zinc‐ion batteries (ZIBs) have emerged as a cost‐effective and safe energy storage technology but have remained a challenge in developing efficient Zn2+ hosting materials for large‐scale applications. The authors have herein designed a ladder‐type dithieno[3,2‐b:2′,3′‐d]pyrrole core twisting hydroquinone or pyrocatechol redox pendants as redox conducting polymer cathodes for highly‐efficient and robust aqueous ZIBs. The impact of pendant configuration on the energy level, Zn2+ hosting behavior, and battery performance of these polymer electrodes are systematically investigated. Experimental and theoretical studies clearly reveal the outstanding molecular planarity and highly reversible redox reaction for hydroquinone‐derived PDpBQ cathode, which can effectively tackle the bottleneck problems for ZIBs on aspects of structural stability and Zn2+ insertion/extraction dynamics. Steady capacity output upon 120 mAh g−1 is achieved with considerable rate performance (52.5% of capacity retention at 5 A g−1), while pyrocatechol‐derived polymer PDoBQ exhibits a sharply fading redox responsiveness (over 45%) due to restricted charge transfer and unselective zinc‐ion capturing nature. This molecular design of highly conductive backbone twisting redox pendants with planar molecular plane and specific Zn2+ hosting as polymer cathodes demonstrates an effective strategy for high‐performance and robust ZIBs.
A Prevascularized Polyurethane‐Reinforced Fibrin Patch Improves Regenerative Remodeling in a Rat Right Ventricle Replacement Model
Authors: Tao Ze‐Wei , Jarrell Dillon K. , Robinson Andrew , Cosgriff‐Hernandez Elizabeth M. , Jacot Jeffrey G. 
Published: October 2021

AbstractCongenital heart defects (CHDs) affect 1 in 120 newborns in the United States. Surgical repair of structural heart defects often leads to arrhythmia and increased risk of heart failure. The laboratory has previously developed an acellular fibrin patch reinforced with a biodegradable poly(ether ester urethane) urea mesh that result in improved heart function when tested in a rat right ventricle wall replacement model compared to fixed pericardium. However, this patch does not drive significant neotissue formation. The patch materials are modified here and this patch is prevascularized with human umbilical vein endothelial cells and c‐Kit+ human amniotic fluid stem cells. Rudimentary capillary‐like networks form in the fibrin after culture of cell‐encapsulated patches for 3 d in vitro. Prevascularized patches and noncell loaded patch controls are implanted onto full‐thickness heart wall defects created in the right ventricle of athymic nude rats. Two months after surgery, defect repair with prevascularized patches results in improved heart function and the patched heart area exhibited greater vascularization and muscularization, less fibrosis, and increased M2 macrophage infiltration compared to acellular patches.
Superior High‐Temperature Strength in a Supersaturated Refractory High‐Entropy Alloy
Authors: Feng Rui , Feng Bojun , Gao Michael C. , Zhang Chuan , Neuefeind Joerg C. , Poplawsky Jonathan D. , Ren Yang , An Ke , Widom Michael , Liaw Peter K. 
Published: October 2021

AbstractRefractory high‐entropy alloys (RHEAs) show promising applications at high temperatures. However, achieving high strengths at elevated temperatures above 1173K is still challenging due to heat softening. Using intrinsic material characteristics as the alloy‐design principles, a single‐phase body‐centered‐cubic (BCC) CrMoNbV RHEA with high‐temperature strengths (beyond 1000 MPa at 1273 K) is designed, superior to other reported RHEAs as well as conventional superalloys. The origin of the high‐temperature strength is revealed by in situ neutron scattering, transmission‐electron microscopy, and first‐principles calculations. The CrMoNbV's elevated‐temperature strength retention up to 1273 K arises from its large atomic‐size and elastic‐modulus mismatches, the insensitive temperature dependence of elastic constants, and the dominance of non‐screw character dislocations caused by the strong solute pinning, which makes the solid‐solution strengthening pronounced. The alloy‐design principles and the insights in this study pave the way to design RHEAs with outstanding high‐temperature strength.
Conjugated Polyelectrolytes: Underexplored Materials for Pseudocapacitive Energy Storage
Authors: Quek Glenn , Roehrich Brian , Su Yude , Sepunaru Lior , Bazan Guillermo C. 
Published: October 2021

AbstractConjugated polyelectrolytes (CPEs) are characterized by an electronically delocalized backbone bearing ionic functionalities. These features lead to properties relevant for use in energy‐storing pseudocapacitor devices, including ionic conductivity, water processability, gel‐formation, and formation of polaronic species stabilized by electrostatic interactions. In this Perspective, the basis for evaluating the figures of merit for pseudocapacitors is provided, together with the techniques used for their evaluation. The general utility and challenges encountered with neutral conjugated polymers are then discussed. Finally, recent advances on the use of CPEs in pseudocapacitor devices are reviewed. The article is concluded by discussing how their miscibility in aqueous media permits the incorporation of CPEs in living materials that are capable of switching function from extraction of energy from bacterial metabolic pathways to pseudocapacitor energy storage.
Surface‐Dependent Intermediate Adsorption Modulation on Iridium‐Modified Black Phosphorus Electrocatalysts for Efficient pH‐Universal Water Splitting
Authors: Mei Jun , He Tianwei , Bai Juan , Qi Dongchen , Du Aijun , Liao Ting , Ayoko Godwin A. , Yamauchi Yusuke , Sun Litao , Sun Ziqi 
Published: October 2021

Abstract2D black phosphorus (BP) is one promising electrocatalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysis. The too strong adsorption of oxygen intermediates during OER, while the too weak adsorption of hydrogen intermediate during HER, however, greatly compromise its practical water splitting applications with overpotentials as high as 450 mV for OER and 420 mV for HER to achieve 10 mA cm−2 under alkaline conditions. Herein, by rationally introducing the nanosized iridium (Ir) modifier together with optimized exposing surface toward electrolytes, an efficient Ir‐modified BP electrocatalyst with much favorable adsorption energies toward catalytic intermediates possesses an outstanding pH‐universal water splitting performance, surpassing the nearly all reported BP‐based catalysts and the commercial noble‐metal catalysts. The Ir‐modified BP catalyst with the optimized exposed surfaces only requires an overall cell voltage of 1.54 and 1.57 V to achieve 10 mA cm−2 in acidic and alkaline electrolysers, respectively. This design uncovers the potential applications of 2D BP in practical electrocatalysis fields via decreasing reaction intermediate adsorption energy barriers and promoting the interfacial electron coupling for heterostructured catalysts, and offers new insights into the surface‐dependent activity enhancement mechanism.
Dynamically Tuneable Reflective Structural Coloration with Electroactive Conducting Polymer Nanocavities
Authors: Rossi Stefano , Olsson Oliver , Chen Shangzhi , Shanker Ravi , Banerjee Debashree , Dahlin Andreas , Jonsson Magnus P. 
Published: October 2021

AbstractDynamic control of structural colors across the visible spectrum with high brightness has proven to be a difficult challenge. Here, this is addressed with a tuneable reflective nano‐optical cavity that uses an electroactive conducting polymer (poly(thieno[3,4‐b]thiophene)) as spacer layer. Electrochemical doping and dedoping of the polymer spacer layer provides reversible tuning of the cavity's structural color throughout the entire visible range and beyond. Furthermore, the cavity provides high peak reflectance that varies only slightly between the reduced and oxidized states of the polymer. The results indicate that the polymer undergoes large reversible thickness changes upon redox tuning, aided by changes in optical properties and low visible absorption. The electroactive cavity concept may find particular use in reflective displays, by opening for tuneable monopixels that eliminate limitations in brightness of traditional subpixel‐based systems.
An Antipulverization and High‐Continuity Lithium Metal Anode for High‐Energy Lithium Batteries
Authors: Ye Yusheng , Zhao Yuanyuan , Zhao Teng , Xu Sainan , Xu Zhixin , Qian Ji , Wang Lili , Xing Yi , Wei Lei , Li Yuejiao , Wang Jiulin , Li Li , Wu Feng , Chen Renjie 
Published: October 2021

AbstractLithium metal is one of the most promising anode candidates for next‐generation high‐energy batteries. Nevertheless, lithium pulverization and associated loss of electrical contact remain significant challenges. Here, an antipulverization and high‐continuity lithium metal anode comprising a small number of solid‐state electrolyte (SSE) nanoparticles as conformal/sacrificial fillers and a copper (Cu) foil as the supporting current collector is reported. Guiding by the SSE, this new anode facilitates lithium nucleation, contributing to form a roundly shaped, micro‐sized, and dendrite‐free electrode during cycling, which effectively mitigates the lithium dendrite growth. The embedded Cu current collector in the hybrid anode not only reinforces the mechanical strength but also improves the efficient charge transfer among active lithium filaments, affording good electrode structural integrity and electrical continuity. As a result, this antipulverization and high‐continuity lithium anode delivers a high average Coulombic efficiency of ≈99.6% for 300 cycles under a current density of 1 mA cm−2. Lithium–sulfur batteries (elemental sulfur or sulfurized polyacrylonitrile cathodes) equipped with this anode show high‐capacity retentions in their corresponding ether‐based or carbonate‐based electrolytes, respectively. This new electrode provides important insight into the design of electrodes that may experience large volume variation during operations.
Enzymatically Transformable Polymersome‐Based Nanotherapeutics to Eliminate Minimal Relapsable Cancer
Authors: Li Junjie , Ge Zhishen , Toh Kazuko , Liu Xueying , Dirisala Anjaneyulu , Ke Wendong , Wen Panyue , Zhou Hang , Wang Zheng , Xiao Shiyan , Van Guyse Joachim F. R. , Tockary Theofilus A. , Xie Jinbing , Gonzalez‐Carter Daniel , Kinoh Hiroaki , Uchida Satoshi , Anraku Yasutaka , Kataoka Kazunori 
Published: October 2021

AbstractPrevention of metastatic and local‐regional recurrence of cancer after surgery remains difficult. Targeting postsurgical premetastatic niche and microresiduals presents an excellent prospective opportunity but is often challenged by poor therapeutic delivery into minimal residual tumors. Here, an enzymatically transformable polymer‐based nanotherapeutic approach is presented that exploits matrix metalloproteinase (MMP) overactivation in tumor‐associated tissues to guide the codelivery of colchicine (microtubule‐disrupting and anti‐inflammatory agent) and marimastat (MMP inhibitor). The dePEGylation of polymersomes catalyzed by MMPs not only exposes the guanidine moiety to improve tissue/cell‐targeting/retention to increase bioavailability, but also differentially releases marimastat and colchicine to engage their extracellular (MMPs) and intracellular (microtubules) targets of action, respectively. In primary tumors/overt metastases, the vasculature‐specific targeting of nanotherapeutics can function synchronously with the enhanced permeability and retention effect to deter malignant progression of metastatic breast cancer. After the surgical removal of large primary tumors, nanotherapeutic agents are localized in the premetastatic niche and at the site of the postsurgical wound, disrupting the premetastatic microenvironment and eliminating microresiduals, which radically reduces metastatic and local‐regional recurrence. The findings suggest that nanotherapeutics can safely widen the therapeutic window to resuscitate colchicine and MMP inhibitors for other inflammatory disorders.
Ionic Covalent Organic Frameworks for Energy Devices
Authors: Liang Xiaoguang , Tian Ye , Yuan Yufei , Kim Yoonseob 
Published: October 2021

AbstractCovalent organic frameworks (COFs) are a class of porous crystalline materials whose facile preparation, functionality, and modularity have led to their becoming powerful platforms for the development of molecular devices in many fields of (bio)engineering, such as energy storage, environmental remediation, drug delivery, and catalysis. In particular, ionic COFs (iCOFs) are highly useful for constructing energy devices, as their ionic functional groups can transport ions efficiently, and the nonlabile and highly ordered all‐covalent pore structures of their backbones provide ideal pathways for long‐term ionic transport under harsh electrochemical conditions. Here, current research progress on the use of iCOFs for energy devices, specifically lithium‐based batteries and fuel cells, is reviewed in terms of iCOF backbone‐design strategies, synthetic approaches, properties, engineering techniques, and applications. iCOFs are categorized as anionic COFs or cationic COFs, and how each of these types of iCOFs transport lithium ions, protons, or hydroxides is illustrated. Finally, the current challenges to and future opportunities for the utilization of iCOFs in energy devices are described. This review will therefore serve as a useful reference on state‐of‐the‐art iCOF design and application strategies focusing on energy devices.
Conductive CuCo‐Based Bimetal Organic Framework for Efficient Hydrogen Evolution
Authors: Geng Bo , Yan Feng , Zhang Xiao , He Yuqian , Zhu Chunling , Chou Shu‐Lei , Zhang Xiaoli , Chen Yujin 
Published: October 2021

AbstractMetal–organic frameworks (MOFs) with intrinsically porous structures and well‐dispersed metal sites are promising candidates for electrocatalysis; however, the catalytic efficiencies of most MOFs are significantly limited by their impertinent adsorption/desorption energy of intermediates formed during electrocatalysis and very low electrical conductivity. Herein, Co is introduced into conductive Cu‐catecholate (Cu‐CAT) nanorod arrays directly grown on a flexible carbon cloth for hydrogen evolution reaction (HER). Electrochemical results show that the Co‐incorporated Cu‐CAT nanorod arrays only need 52 and 143 mV overpotentials to drive a current density of 10 mA cm−2 in alkaline and neutral media for HER, respectively, much lower than most of the reported non‐noble metal‐based electrocatalysts and comparable to the benchmark Pt/C electrocatalyst. Density functional theory calculations show that the introduction of Co can optimize the adsorption energy of hydrogen (ΔGH*) of Cu sites, almost close to that of Pt (111). Furthermore, the adsorption energy of water () of Co sites in the CuCo‐CAT is significantly lower than that of Cu sites upon coupling Cu with Co, effectively accelerating the Volmer step in the HER process. The findings, synergistic effect of bimetals, open a new avenue for the rational design of highly efficient MOF‐based electrocatalysts.
Biphasic Porous Structures formed by Monomer/Water Interface Stabilization with Colloidal Nanoparticles
Authors: Pizzetti Fabio , Rossetti Arianna , Marchetti Alessandro , Castiglione Franca , Vanoli Valeria , Coste Elena , Veneruso Valeria , Veglianese Pietro , Sacchetti Alessandro , Cingolani Alberto , Rossi Filippo 
Published: October 2021

AbstractBicontinuous jammed emulsions (known as bijels) are Pickering emulsions where oil and water are both continuous phases. These interconnected structures, stabilized by colloidal nanoparticles at the oil–water interface, have been used in a wide range of applications. Among these, catalysis and encapsulation of solutes has showed promising potential, but the low mechanical properties of the systems limit their use. Here it is proposed that the use of a hydrophobic monomer able to polymerize in bulk and form a biphasic porous structure with polymer and water as immiscible phases. The final system is stabilized by colloidal nanoparticles made of hydroxyapatite, and the system's ability to release both hydrophilic and hydrophobic drugs has been demonstrated. The strategy has been proven to be highly versatile and may be tuned with a diversity of monomers and nanoparticles to satisfy specific industrial and medical needs.
Enhancing Mechanical Energy Transfer of Piezoelectric Supercapacitors
Authors: Jadhav Sagar , Pham Hong Duc , Padwal Chinmayee , Chougale Mahesh , Brown Cameron , Motta Nunzio , Ostrikov Kostya (Ken) , Bae Jinho , Dubal Deepak 
Published: October 2021

AbstractThe expected widespread use of wearable and other low‐power healthcare devices has triggered great interest in piezoelectric materials as a promising energy harvester. However, traditional piezoelectric materials suffer from poor interfacial energy transfer when used in self‐charging power cells. Herein, piezoelectric supercapacitors (PSCs) are engineered using MXene‐incorporated polymeric piezo separator and MXene (Ti3C2Tx) multilayered sheets as electrodes. The MXene‐blended polymer film showed considerable improvement with maximum output voltage of 28 V and current of 1.71 µA. The electromechanical properties studied by piezoelectric force microscopy suggest that the integration of MXene in polyvinylidene fluoride (PVDF) matrix induces the degree of dipole moment alignment, thereby improving the piezoelectric properties of PVDF. At the device level, the PSC featured the capacitance of 61 mF cm–2, the energy density of 24.9 mJ cm−2, the maximum power density of 1.3 mW cm−3, and the excellent long‐term cycling stability. A way is paved toward green, integrated energy harvesting and storing technology for next‐generation self‐powered implantable and wearable electronics.
Injection Molding of Soft Robots
Authors: Bell Michael A. , Becker Kaitlyn P. , Wood Robert J. 
Published: October 2021

AbstractTo date, injection molding has not been a practical manufacturing method for soft robots due to machine costs, large volumes of liquid silicones required, and the inability to change materials quickly between shots. Injection molds are typically machined from metals to allow for high pressure and clamping forces, which further limits the ability to rapidly prototype soft robots when molds could cost thousands of dollars. To circumvent these issues, a low‐cost injection molding system and process are pioneered. In this article, the apparatus, design process, economics, and workflow are described using standard stereolithography and polyjet 3D printers to rapidly iterate on soft robot designs. The mold design process is further detailed to allow for proper material flow, clamping, alignment, and rapid curing times. Static mixing nozzle efficacy is characterized with common silicone materials compared to manual mixing and centrifugal planetary mixing. Lastly, a number of applications that could only be achieved through injection molding due to geometry, embedded components, or cure times are presented.