bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficacy, Safety, and Sample Quality of Ultrasound‐Guided Synovial Needle Biopsy in Clinical Practice and Research: A Prospective Observational Study
Authors: Romão Vasco C. , Polido‐Pereira Joaquim , Barros Rita , Luís Rita , Vidal Bruno , Vieira‐Sousa Elsa , Vitorino Emília , Humby Frances , Kelly Stephen , Pitzalis Costantino , Saraiva Fernando , Fonseca João Eurico
Published: August 2019

Objective

To study the efficacy, tolerability, safety, and sampling variation of ultrasound (US)–guided synovial biopsies performed in clinical practice and research.

Methods

We included all patients who had a US‐guided synovial needle biopsy from November 2013 to January 2018. Patients were evaluated for procedure safety and tolerability. Usefulness of synovial biopsy was considered based on contribution for achieving the proposed aims. We analyzed samples for presence and quality of synovial tissue, synovitis score/grade, and pathotype. Variation across patients, samples, section levels, and sampling order was assessed.

Results

A total of 64 US‐guided synovial biopsies were performed (n = 52 in clinical practice, n = 12 in research). Patient tolerability (70% no/mild discomfort) was remarkably high. There was no significant aggravation of symptoms or US synovitis in the biopsied joint. Procedures were overall safe, with few minor, 2 moderate, and no major adverse events. Usefulness of US‐guided synovial biopsies was high, both in clinical practice (37% direct diagnostic impact, 100% positive/95% negative predictive values for infection) and in research (92% success). Synovial tissue was retrieved in 88% of biopsies, with a median of 75% gradable samples. There was significant variation in sample quality and synovitis features across patients and samples, but not between different section levels. Samples collected later in the procedure had a lower frequency of synovial tissue and were poorly concordant in pathotype with those collected earlier.

Conclusion

US‐guided synovial needle biopsy is an effective, safe, and well‐tolerated means to collect good quality synovial tissue for clinical and research purposes. Samples collected for different aims should be retrieved in parallel, rather than sequentially.
Association Between Participant Retention and the Proportion of Included Elderly People in Rheumatology Trials: Results From a Series of Exploratory Meta‐Regression Analyses
Authors: Palmowski Andriko , Nielsen Sabrina M. , Buttgereit Thomas , Palmowski Yannick , Boers Maarten , Christensen Robin , Buttgereit Frank
Published: August 2019

Objective

The elderly, a population defined by an age of ≥65 years, are underrepresented in rheumatology trials, possibly due to investigators’ concerns of increased premature discontinuations in higher age groups. The present study was undertaken to evaluate whether the proportion of included elderly individuals (PE) is independently associated with participant retention in rheumatology trials.

Methods

Medline was searched for randomized controlled trials (RCTs) in rheumatoid arthritis (RA) and osteoarthritis (OA) of any intervention (years 2016 and 2017). PE was either extracted from the research manuscript or estimated from an assumed (truncated) normal distribution. We used mixed‐effects meta‐regression models including several covariates to assess whether there is an independent association between PE and participant retention. Using sensitivity analyses, we evaluated whether associations were connected to attrition due to lack of efficacy (LoE) or adverse events (AE).

Results

In total, 243 RCTs comprising >48,000 participants were included. Pooled participant retention was 88%. PE was not associated with retention in the unadjusted (P = 0.97) or adjusted (all: P ≥ 0.14) models. Of all covariates, only study duration and type of intervention were associated with retention (both: P < 0.001). Post hoc analyses allowing for interaction revealed a small but statistically significant positive association between PE and retention in pharmacologic interventions and a negative association in physical/physiotherapeutic interventions (overall P for interaction = 0.05). No associations were found for PE and attrition due to LoE or AE.

Conclusion

Participant retention in RA and OA trials is high and not associated with PE. These findings should motivate investigators to include more elderly participants in rheumatology trials.
Longitudinal Study of Fatigue, Stress, and Depression: Role of Reduction in Stress Toward Improvement in Fatigue
Authors: Azizoddin Desiree R. , Jolly Meenakshi , Arora Shilpa , Yelin Edward , Katz Patricia
Published: August 2019

Objective

Fatigue is common among individuals with systemic lupus erythematosus (SLE), but the causes are not well understood. Our objective was to examine perceived stress and depressive symptoms as predictors of fatigue in SLE.

Methods

Data from 2 years of the Lupus Outcomes Study (n = 650 patients), obtained through annual structured interviews, were used. Fatigue was measured with the Short Form 36 (SF‐36) vitality scale along with a variety of self‐report measures of disease, depression, and stress. Multivariate linear regression models examined predictors of changes in fatigue. Model 1 tested the association of time 1 (T1) depression with time 2 (T2) fatigue; model 2 added T1 perceived stress to model 1, and final models added T1‐to‐T2 decrease in stress. All analyses controlled for T1 fatigue, age, sex, self‐report of fibromyalgia, pain, and SLE duration, activity, and damage.

Results

Mean ± SD age was 51 ± 12 years, 92% of participants were women, and 68% were white. The mean ± SD SF‐36 fatigue score was 55 ± 24. T1 depression significantly predicted T2 fatigue. When T1 stress was added, stress (β = 1.7 [95% confidence interval (95% CI) 1.1, 2.2]; P < 0.0001) significantly predicted T2 fatigue, but depression was no longer significant. The addition of T1‐to‐T2 decrease in stress was associated with a clinically meaningful decline in fatigue (β = –11.8 [95% CI –15.6, –8.9]; P < 0.0001).

Conclusion

While depressive symptoms initially predicted subsequent fatigue, the effects were mediated by stress. A decrease in stress, in addition, was associated with a clinically meaningful decrease in fatigue. These results suggest that perceived stress plays an important role in SLE fatigue and may be an important focus of interventions for fatigue.
Can Patient‐Reported Symptoms Be Used to Measure Disease Activity in Systemic Sclerosis?
Authors: Ross Laura , Stevens Wendy , Wilson Michelle , Strickland Gemma , Walker Jennifer , Sahhar Joanne , Ngian Gene-Siew , Roddy Janet , Major Gabor , Proudman Susanna , Baron Murray , Nikpour Mandana
Published: August 2019

Objective

To evaluate the association between patient‐reported symptoms and changes in disease activity over time in systemic sclerosis (SSc).

Methods

Using data from 1,636 patients enrolled in the Australian Scleroderma Cohort Study, we used generalized estimating equations to determine the relationship between patient‐reported worsening of Raynaud’s phenomenon (RP), skin involvement, and breathlessness in the month preceding each study visit and features of disease activity in the corresponding organ systems. The associations between the following parameters were analyzed: patient‐reported worsening RP and the presence of new‐onset digital pitting and digital ulcers; patient‐reported worsening skin involvement and increasing modified Rodnan skin thickness score (MRSS); new areas of skin involvement and new‐onset joint contractures; patient‐reported worsening breathlessness and deteriorating respiratory functions test (RFT) results, indicated by a 10% decrease in forced vital capacity (FVC) and a 15% decrease in diffusing capacity for carbon monoxide (DLco), new‐onset interstitial lung disease (ILD), and new‐onset pulmonary arterial hypertension (PAH).

Results

We found a significant association between patient‐reported worsening RP and the presence of digital ulcers (odds ratio [OR] 1.53 [95% confidence interval (95% CI) 0.60–0.93]), patient‐reported worsening skin involvement and increasing MRSS (OR 2.10 [95% CI 1.54–2.86]), and worsening patient breathlessness and deteriorating RFTs (FVC OR 2.12 [95% CI 1.70–2.65]; DLco OR 1.97 [95% CI 1.34–2.02]), new‐onset ILD (OR 1.91 [95% CI 1.40–2.61]), and new‐onset PAH (OR 5.08 [95% CI 3.59–7.19]).

Conclusion

These results demonstrate that patient‐reported symptoms are associated with clinically meaningful changes in disease activity in patients with SSc. This suggests that when objective measures of change in disease status are unavailable, patient‐reported symptoms could be used to indicate a change in SSc disease activity.
Covalent Organic Framework‐Supported Molecularly Dispersed Near‐Infrared Dyes Boost Immunogenic Phototherapy against Tumors
Authors: Gan Shaoju , Tong Xiaoning , Zhang Yue , Wu Jinhui , Hu Yiqiao , Yuan Ahu
Published: August 2019

Photodynamic therapy (PDT) mediated by near‐infrared (NIR) dyes is a promising cancer treatment modality; however, its use is limited by significant challenges, such as hypoxic tumor microenvironments and self‐quenching of photosensitizers. These challenges hamper its utility in inducing immunogenic cell death (ICD) and triggering potent systemic antitumor immune responses. This study demonstrates that molecular dispersion of NIR dyes in nanocarriers can significantly enhance their ability to produce reactive oxygen species and potentiate synergistic PDT and photothermal therapy against tumors. Specifically, NIR dye indocyanine green (ICG) can be spontaneously adsorbed to covalent organic frameworks (COFs) via π–π conjugations to prevent intermolecular stacking interactions. Then, ICG‐loaded COFs are ultrasonically exfoliated and coated with polydopamine (PDA) to construct a new phototherapeutic agent ICG@COF‐1@PDA with enhanced efficacy. In conjunction with ICG@COF‐1@PDA, a single round of NIR laser irradiation can induce obvious ICD, elicit antitumor immunity in colorectal cancer, and yield 62.9% inhibition of untreated distant tumors. ICG@COF‐1@PDA also exhibits notable phototherapeutic efficacy against 4T1 murine breast to lung metastasis, a spontaneous metastasis mode for triple‐negative breast cancers (TNBCs). Overall, this study reveals a novel nanodelivery system for molecular dispersion of NIR dyes, which may present new therapeutic opportunities against primary and metastatic tumors.
Graphdiyne: A New Photocatalytic CO2 Reduction Cocatalyst
Authors: Xu Feiyan , Meng Kai , Zhu Bicheng , Liu Huibiao , Xu Jingsan , Yu Jiaguo
Published: August 2019

Exploring new and efficient cocatalysts to boost photocatalytic CO2 reduction is of critical importance for solar‐to‐fuel conversion. As an emerging carbon allotrope, graphdiyne (GDY) features 2D characteristics and unique carbon–carbon bonds. Herein, a novel GDY cocatalyst coupled TiO2 nanofibers for boosted photocatalytic CO2 reduction, synthesized by an electrostatic self‐assembly approach is reported. First‐principle calculation and in situ X‐ray photoelectron spectroscopy measurement reveal that the delocalized electrons in GDY can hybrid with the empty orbitals in TiO2 within the TiO2/GDY network, leading to the formation of an internal electric field at the interfaces, pointing from GDY to TiO2. The theoretical simulation further implies strong chemisorption and deformation of CO2 molecules upon GDY, which can be verified by in situ diffuse reflectance infrared Fourier transform spectroscopy. These effects, in combination with the photothermal effect of GDY, result in enhanced charge separation and directed electron transfer, enhanced CO2 adsorption and activation as well as accelerated catalytic reactions over the TiO2/GDY heterostructure, thereby resulting in significantly improved CO2 photoreduction efficiency and meanwhile with remarkable selectivity. This work demonstrates that GYD can function as a highly effective cocatalyst for solar energy harvesting and may be used in other catalysis processes.
Efficient Cesium Lead Halide Perovskite Solar Cells through Alternative Thousand‐Layer Rapid Deposition
Authors: Lin Hung‐Yu , Chen Chien‐Yu , Hsu Bo‐Wei , Cheng Yu‐Lun , Tsai Wei‐Lun , Huang Yu‐Ching , Tsao Cheng‐Si , Lin Hao‐Wu
Published: August 2019

The novel growth of cesium lead halide perovskite thin films, which are prepared through thousand‐layer rapid alternative deposition, is performed by developing an active perovskite film consisting of a layer‐by‐layer structure. This method is considerably more difficult to be implemented from the solution process. The obtained thin film morphology and characteristics are distinguished from that of the traditional a few layers and two‐material codeposition. These alternative deposited perovskites are integrated with vacuum‐deposited carrier‐transporting layers and electrodes, and all vacuum‐sublimed perovskite solar cells exhibit an outstanding power conversion efficiency of 13.0%. The use of these devices for environmental light energy harvesting provides a power conversion efficiency of 33.9% under fluorescent light illumination of 1000 lux.
Hole Transport Bilayer Structure for Quasi‐2D Perovskite Based Blue Light‐Emitting Diodes with High Brightness and Good Spectral Stability
Authors: Ren Zhenwei , Xiao Xiangtian , Ma Ruiman , Lin Hong , Wang Kai , Sun Xiao Wei , Choy Wallace C. H.
Published: August 2019

Substantial achievements have been made in green and red perovskite light emitting diodes (PeLEDs) recently. However, blue PeLEDs still lag behind with much lower performances. One of the main reasons is the mass undesirable nonradiative recombination at interfaces and within the perovskite films. In this work, an efficient hole transport bi‐layer structure composed of PSSNa and NiOx is demonstrated to simultaneously inhibit the nonradiative decays between NiOx and perovskite films by reducing NiOx surface defects and improving quasi‐2D perovskite thin film quality by minimizing its pin‐holes and reducing the film roughness. The results show that the dipole feature of PSSNa improves the hole transportation and thus PeLED performances. Moreover, by introducing KBr into the perovskite, its film quality improves and trap states reduce. Eventually, the blue PeLEDs is achieved with a very low turn‐on voltage of 3.31 V accompanied with an external quantum efficiency of 1.45% and a remarkable luminance of 4359 cd m‐2. With further optimization of the perovskite precursor concentration, the highest luminance reaches 5737 cd m‐2, which represents the brightest blue PeLEDs reported to date as far as it is known. Furthermore, the devices also show better spectral stability and operation lifetime as compared to other blue PeLEDs.
Breaking Reciprocity with Space‐Time‐Coding Digital Metasurfaces
Authors: Zhang Lei , Chen Xiao Qing , Shao Rui Wen , Dai Jun Yan , Cheng Qiang , Castaldi Giuseppe , Galdi Vincenzo , Cui Tie Jun
Published: August 2019

Metasurfaces are artificially engineered ultrathin structures that can finely tailor and control electromagnetic wavefronts. There is currently a strong interest in exploring their capability to lift some fundamental limitations dictated by Lorentz reciprocity, which have strong implications in communication, heat management, and energy harvesting. Time‐varying approaches have emerged as attractive alternatives to conventional schemes relying on magnetic or nonlinear materials, but experimental evidence is currently limited to devices such as circulators and antennas. Here, the recently proposed concept of space‐time‐coding digital metasurfaces is leveraged to break reciprocity. Moreover, it is shown that such nonreciprocal effects can be controlled dynamically. This approach relies on inducing suitable spatiotemporal phase gradients in a programmable way via digital modulation of the metasurface‐elements' phase repsonse, which enable anomalous reflections accompanied by frequency conversions. A prototype operating at microwave frequencies is designed and fabricated for proof‐of‐concept validation. Measured results are in good agreement with theory, hence providing the first experimental evidence of nonreciprocal reflection effects enabled by space‐time‐modulated digital metasurfaces. The proposed concept and platform set the stage for “on‐demand” realization of nonreciprocal effects, in programmable or reconfigurable fashions, which may find several promising applications, including frequency conversion, Doppler frequency illusion, optical isolation, and unidirectional transmission.
Two in One: Light as a Tool for 3D Printing and Erasing at the Microscale
Authors: Batchelor Rhiannon , Messer Tobias , Hippler Marc , Wegener Martin , Barner‐Kowollik Christopher , Blasco Eva
Published: August 2019

The ability to selectively remove sections from 3D‐printed structures with high resolution remains a current challenge in 3D laser lithography. A novel photoresist is introduced to enable the additive fabrication of 3D microstructures at one wavelength and subsequent spatially controlled cleavage of the printed resist at another wavelength. The photoresist is composed of a difunctional acrylate cross‐linker containing a photolabile o‐nitrobenzyl ether moiety. 3D microstructures are written by photoinduced radical polymerization of acrylates using Ivocerin as photoinitiator upon exposure to 900 nm laser light. Subsequent scanning using a laser at 700 nm wavelength allows for the selective removal of the resist by photocleaving the o‐nitrobenzyl group. Both steps rely on two‐photon absorption. The fabricated and erased features are imaged using scanning electron microscopy (SEM) and laser scanning microscopy (LSM). In addition, a single wire bond is successfully eliminated from an array, proving the possibility of complete or partial removal of structures on demand.
Elemental Nanoanalysis of Interfacial Alumina–Aryl Fluoride Interactions in Fullerene‐Free Organic Tandem Solar Cells
Authors: Hoefler Sebastian F. , Haberfehlner Georg , Rath Thomas , Canteri Roberto , Barozzi Mario , Hofer Ferdinand , Trimmel Gregor
Published: August 2019

The choice of the optimum combination of materials for the absorber layers, electrodes, as well as interfacial layers is highly important to enhance further advances in the field of organic photovoltaics. Usually, these materials are assumed to be stable under the applied processing steps for the fabrication of the solar cells. Herein, organic tandem solar cells are examined with fluorine‐containing absorber layers consisting of the fluorinated polymer donor PTB7‐Th and the indacenodithiophene‐type small molecule acceptor O‐IDTBR and MoO3/Al/PFN‐Br as recombination layer. Although both subcells comprise the same low bandgap absorber materials, the tandem solar cells reveal high open‐circuit voltage values approaching 2 V. However, using a combination of scanning transmission electron microscopy nanoanalysis techniques and secondary ion mass spectrometry with depth profiling, an unexpected phenomenon is disclosed. It is found that significant amounts of fluorine are accumulated in the recombination layer region which originates very likely from alumina–aryl fluoride interactions responsible for a partial defluorination of the conjugated polymer in the absorber layer.
Silver‐Nanoparticle‐Modified Polyimide for Multiple Artificial Skin‐Sensing Applications
Authors: Bi Peng , Liu Xiaowei , Yang Yang , Wang Ziyu , Shi Jing , Liu Gaomin , Kong Fangfang , Zhu Benpeng , Xiong Rui
Published: August 2019

Wearable devices have become very important for collecting health information and monitoring the condition of seriously ill patients. However, most recently developed wearable devices can only monitor limited signals within a very small range of values. A novel sensor is fabricated by modifying the surface of polyimide nanowires with silver nanoparticles. These nanowire sensors can sense both pressure and temperature changes and have antimicrobial properties. The fabricated sensor can detect a wide range of pressure variation from 5 KPa to 100 KPa. A theoretical model is developed to explain the sensing mechanism of the silver‐nanoparticle‐modified polyimide nanowires. The experimental and theoretical results for the nanowires are in good agreement. By attaching these sensors to human joints and fingers, real‐time information can be detected for human motion, such as walking or holding a hot cup of water. The excellent performance of this device shows that it has great potential for use in artificial skins for detecting temperature and human motion.
Soft Material‐Enabled, Active Wireless, Thin‐Film Bioelectronics for Quantitative Diagnostics of Cervical Dystonia
Authors: Kwon Young‐Tae , Lee Yongkuk , Berkmen Gamze Kilic , Lim Hyo‐Ryoung , Scorr Laura , Jinnah Hyder A. , Yeo Woon‐Hong
Published: August 2019

Recent advances in flexible materials, nanomanufacturing, and system integration have provided a great opportunity to develop wearable flexible hybrid electronics for human healthcare, diagnostics, and therapeutics. However, existing medical devices still rely on rigid electronics with many wires and separate components, which hinders wireless, comfortable, continuous monitoring of health‐related human motions. Advanced materials and system integration technologies are introduced that enable soft, active wireless, thin‐film bioelectronics. This low‐modulus, highly flexible wearable electronic system incorporates a nanomembrane wireless circuit and functional chip components enclosed by a soft elastomeric membrane. It can be gently and seamlessly mounted on the skin, while offering comfortable, highly sensitive and accurate detection of head movements. The wireless, skin‐like bioelectronic system (SKINTRONICS) is utilized for quantitative diagnostics of cervical dystonia (CD), which is characterized by involuntary abnormal head postures and repetitive head movements, sometimes with neck muscle pain. A set of analytical and experimental studies shows a soft system packaging, hard–soft materials integration, and quantitative assessment of physiological signals detected by the SKINTRONICS. In vivo demonstration, involving 10 human subjects, finds the device feasible for use in CD measurement.
Hydrophobic, Structure‐Tunable Cu Nanowire@Graphene Core–Shell Aerogels for Piezoresistive Pressure Sensing
Authors: Wu Shiting , Zou Mingchu , Shi Xiaowei , Yuan Yongjun , Bai Wangfeng , Ding Mingye , Cao Anyuan
Published: August 2019

Copper nanowires (CuNWs) are highly conductive yet low‐cost nanostructures for constructing piezoresistive pressure sensors. Rational design and controllable fabrication are essential steps toward high‐performance CuNW‐based sensors, and the oxidation tendency of CuNWs must be inhibited. Conducting and flexible CuNW@graphene (CuNW@G) core–shell aerogels are fabricated with tunable microstructures via a simple assembly followed by thermal annealing, in which the aerogel bulk density, surface wettability, Young's modulus, and electrical conductivity can be adjusted accordingly by varying the initial CuNW dispersion concentration. In particular, these core–shell aerogels convert from hydrophobic to superhydrophobic at higher CuNW concentration with reduced adhesion to water. In the range of investigated CuNW dispersion concentration, the chemical constituent and structure of as‐produced graphene shell is nearly the same, as is the aerogel's antioxidation stability. Based on the piezoresistivity of the core–shell aerogels, flexible pressure sensors operated at a bias voltage of 0.1 V are demonstrated, which can detect compressive stress as low as 640 Pa and exhibit fast response time less than 16 ms. Furthermore, polydimethylsiloxane‐encapsulated CuNW@G aerogels show an enhanced response and higher reversibility. A general and scalable strategy for developing aerogel‐typed piezoresistive pressure sensors with stable performance and low cost is presented.
A Structured Design for Highly Stretchable Electronic Skin
Authors: Zhao Jinsheng , Zhang Can , Zou Dan , Liu Xiaokun , Cai Lixun , Li Xiangyu , Shi Mingxing
Published: August 2019

The sensation of pressure is at the core of haptics, and can be achieved by pressure sensors in an electronic skin. Although a number of multifunctional sensors can be fabricated by adopting diverse microstructures and functional materials, achieving electronic skin with superior sensing capabilities under large‐scale deformations is challenging. A highly stretchable electronic skin based on a structured design is proposed and fabricated. It exhibits stable response and long‐term durability in sensing pressure due to improved strain isolation and restrained interfacial failure, in situations nearly regardless of what large‐scale deformations the electronic skins may undergo, such as stretching, bending, or even twisting. Experimental studies and finite element analyses show that their mechanical properties allow these electronic skins to function during large motions including bending states of fingers and wrists. The advanced development of electronic skin demonstrates potential applications in intelligent robots, bionic prostheses, health monitoring, human–machine interfaces, and other fields.
An Imperceptible Magnetic Skin
Authors: Almansouri Abdullah S. , Alsharif Nouf A. , Khan Mohammed A. , Swanepoel Liam , Kaidarova Altynay , Salama Khaled N. , Kosel Jurgen
Published: August 2019

Flexible and wearable magnetoelectronics add intriguing new functionalities to natural perception. Of particular interest regarding these artificial skins are wireless sensing and touchless interactions. Biocompatibility and imperceptibility are the most significant features of devices attached to the bodies. A biocompatible magnetic skin is introduced. It offers extreme flexibility, stretchability (>300%), and is lightweight, while maintaining a remanent magnetization up to 360 mT. It is comfortable to wear, can be realized in any desired shape or color, and adds tunable permanent magnetic properties to the surface it is applied to. It provides remote control functions and is combined with magnetic sensors; it implements a complete wearable magnetic system. For example, eye tracking is realized by attaching the magnetic skin to the eyelid. The advantage that it does not require any wiring makes it an extremely viable solution for soft robotics and human–machine interactions. Wearing the magnetic skin on a finger or integrated into a glove allows for remote gesture control. This type of application opens the door to new control concepts, relevant for people with disabilities, sterile environments, or the consumer industry.
Direct Synthesis of Dihydropyrrolo[2,1‐a]Isoquinolines through FeCl3 Promoted Oxidative Aromatization
Authors: Cui Hai‐Lei , Jiang Lu , Tan Hao , Liu Si
Published: August 2019

We have developed a straightforward FeCl3 promoted synthesis of dihydropyrrolo[2,1‐a]isoquinolines through formal (3+2) cycloaddition/oxidative aromatization cascade of dihydroisoquinoline with Morita‐Baylis‐Hillman carbonates (up to 96% yield). Further modifications of the obtained products were successful through simple chemical transformations providing a diverse range of natural product‐like molecules (12 examples).

magnified image
Transferrin‐Coated Nanodiamond–Drug Conjugates for Milliwatt Photothermal Applications
Authors: Harvey Sean , Raabe Marco , Ermakova Anna , Wu Yingke , Zapata Todd , Chen Chaojian , Lu Hao , Jelezko Fedor , Ng David Y. W. , Weil Tanja
Published: August 2019

Fluorescent nanodiamonds (fNDs) are unique carbon‐based nanomaterials due to their outstanding optical and magnetic properties. However, realization of the full potential of fNDs is often limited by their processability because fNDs aggregate strongly in both organic and aqueous solutions. Therefore, robust and potentially universal coating strategies are urgently needed to address these limitations. Derived from mussel foot proteins, the polymerization of l‐3,4‐dihydroxyphenylalanine (l‐DOPA) provides important surface functional groups including amines, carboxylic acid, alcohols, and conjugated Michael acceptors. Herein, l‐DOPA is polymerized on fNDs with a high control over the shell thickness. Photoluminescence and optically detected magnetic resonance studies reveal that the unique photophysical properties of fNDs are preserved after thin poly(l‐DOPA) film coating. Subsequently, conjugation of transferrin, a heme protein that provides efficient receptor‐specific cellular transport, improves the colloidal stability and cellular uptake of the poly(l‐DOPA)‐coated fNDs. The loading of FDA‐approved indocyanine green as a photothermal agent yields an integrated biohybrid material exhibiting an amplified photothermal effect in cells at very low energy intake (≈90 mW cm−2).
Bladder Cancer Photodynamic Therapeutic Agent with Off‐On Magnetic Resonance Imaging Enhancement
Authors: Xie Chen , Chau Ho‐Fai , Zhang Jing‐Xiang , Tong Sheng , Jiang Lijun , Fok Wan‐Yiu , Lung Hong‐Lok , Zha Shuai , Zou Rui , Jiao Ju , Ng Chi‐Fai , Ma Ping'an , Zhang Junhui , Lin Jun , Shiu Kwok Keung , Bünzli Jean‐Claude G. , Wong Wai‐Kwok , Long Nicholas J. , Law Ga‐Lai , Wong Ka‐Leung
Published: August 2019

Acting as an extracellular matrix protein receptor, αVβ3 integrin becomes an appealing target for photodynamic therapy of bladder cancer. Here, specific αVβ3‐integrin‐targeting porphyrinato‐gadolinium complexes (Gd‐PEG‐Rn) are demonstrated as off‐on theranostic agents, where Rn are specific peptides. Among them, Gd‐PEG‐R3 shows both impressive phototherapeutic index and robust in vivo magnetic resonance imaging (MRI) signal enhancement. Significant selectivity of Gd‐PEG‐R3 is proven by its high αVβ3 integrin binding affinity in positive bladder cancer cells. All these findings support Gd‐PEG‐R3 as a promising bi‐functional medical agent with both MRI contrasting ability and photodynamic therapeutic potential for curing bladder cancer.
Computationally Assisted Assessment of the Metal‐Organic Framework/Polymer Compatibility in Composites Integrating a Rigid Polymer
Authors: Tavares Sergio Rodrigues , Ramsahye Naseem Ahmed , Adil Karim , Eddaoudi Mohamed , Maurin Guillaume , Semino Rocio
Published: August 2019

Density functional theory (DFT) calculations and subsequent classical molecular dynamics (MD) simulations are combined to build and further characterize the interface structure of three binary metal‐organic framework (MOF)/polymer composite materials made of ultra‐small pore MOFs with distinct surface morphologies, namely, MIL‐69, ftw‐MOF‐ABTC, and ftw‐MOF‐BPTC, and the 6‐FDA‐DAM polymer. It is found that the three composites exhibit percolated or independent microvoids of different degrees of interconnectivity, sizes, and positions at the MOF/polymer interface that contribute to decrease the polymer surface coverage, a signature of a relatively poor adhesion between the two components. The ftw‐MOF‐BPTC‐based composite, however, shows a partial penetration of the polymer in the MOF first pore layer, hinting a slightly higher affinity between the MOF and the polymer. These results suggest that even when considering MOFs surfaces with drastically different morphologies, finding a highly compatible MOF/polymer pair for rigid polymers remains challenging.
Direct Simulation of Ternary Mixture Separation in a ZIF‐8 Membrane at Molecular Scale
Authors: Namsani Sadanandam , Ozcan Aydin , Yazaydın A. Özgür
Published: August 2019

Separation of H2 in a ZIF‐8 membrane from a syngas mixture composed of CO2, H2, and N2 at 300 K and 35 atm is simulated with the concentration gradient driven molecular dynamics (CGD‐MD) method. Steady‐state fluxes are computed to predict the H2 selectivity of the ZIF‐8 membrane using four different flexible force fields developed for ZIF‐8. The permselectivities predicted by the CGD‐MD method are compared with those obtained from the grand canonical Monte Carlo+equilibrium molecular dynamics (GCMC+EMD) approach, which is based on the solution‐diffusion model and widely used to predict permselectivities for mixture separations. The permselectivities obtained by using the CGD‐MD method accurately predict that ZIF‐8 is H2 selective over CO2 and N2. On the other hand, permselectivities predicted with the GCMC+EMD approach are found to be incorrect, that is, ZIF‐8 not selective for H2. The study suggests that a reliable non‐equilibrium molecular dynamics approach should be employed in order to obtain accurate predictions for the permselectivity of a membrane for a multicomponent mixture separation process which happens at moderate or high pressure conditions.
Engineering Lateral Heterojunction of Selenium‐Coated Tellurium Nanomaterials toward Highly Efficient Solar Desalination
Authors: Xing Chenyang , Huang Dazhou , Chen Shiyou , Huang Qichen , Zhou Chuanhong , Peng Zhengchun , Li Jiagen , Zhu Xi , Liu Yizhen , Liu Zhipeng , Chen Houkai , Zhao Jinlai , Li Jiangqing , Liu Liping , Cheng Faliang , Fan Dianyuan , Zhang Han
Published: August 2019

Herein, a core–shell tellurium–selenium (Te–Se) nanomaterial with polymer‐tailed and lateral heterojunction structures is developed as a photothermal absorber in a bionic solar‐evaporation system. It is further revealed that the amorphous Se shell surrounds the crystalline Te core, which not only protects the Te phase from oxidation but also serves as a natural barrier to life entities. The core (Te)–shell (Se) configuration thus exhibits robust stability enhanced by 0.05 eV per Se atom and excellent biocompatibility. Furthermore, high energy efficiencies of 90.71 ± 0.37% and 86.14 ± 1.02% and evaporation rates of 12.88 ± 0.052 and 1.323 ± 0.015 kg m−2 h−1 are obtained under 10 and 1 sun for simulated seawater, respectively. Importantly, no salting out is observed in salt solutions, and the collected water under natural light irradiation possesses extremely low ion concentrations of Na+, K+, Ca2+, and Mg2+ relative to real seawater. Considering the tunable electronic structures, biocompatibilities, and modifiable broadband absorption of the solar spectrum of lateral heterojunction nanomaterials of Te–Se, the way is paved to engineering 2D semiconductor materials with supporting 3D porous hydrophilic materials for application in solar desalination, wastewater treatment, and biomedical ventures.
Fabrication of Efficient and Stable CsPbI3 Perovskite Solar Cells through Cation Exchange Process
Authors: Lau Cho Fai Jonathan , Wang Zhiping , Sakai Nobuya , Zheng Jianghui , Liao Chwen Haw , Green Martin , Huang Shujuan , Snaith Henry J. , Ho‐Baillie Anita
Published: August 2019

Inorganic lead halide perovskites have attracted attention due to their tolerance to higher processing temperature and higher bandgap suitable for tandem solar cell application. Not only do they improve cell stability and efficiency, they also reveal many interesting and un‐anticipated material qualities. This work reports a simple cation exchange growth (CEG) method for fabricating inorganic high‐quality cesium lead iodide (CsPbI3) by adding methylammonium iodide (MAI) additive in the precursor. X‐ray diffraction results reveal a multi‐stage film formation process whereby i) MAPbI3 perovskite first formed that acts as a perovskite template for ii) subsequent ion exchange whereby the MA+ ions in the MAPbI3 are replaced by Cs+ (as temperature ramps up) and iii) form g‐phase perovskite CsPbI3. Optical microscopy, photoluminescence, and electrical characterizations reveal that the CEG process produces high‐quality film with better absorption, uniform and dense film with better interface, lower defects, and better stability. Using the CEG approach, the power conversion efficiency of the best CsPbI3 solar cell is significantly increased up to 14.1% for the device fabricated using 1.0 m MAI additive. The outcome is beneficial for further improvement of inorganic perovskite solar cells and their application in perovskite‐silicon tandem devices.
Bandgap Engineering Enhances the Performance of Mixed‐Cation Perovskite Materials for Indoor Photovoltaic Applications
Authors: Wu Ming‐Ju , Kuo Chien‐Chen , Jhuang Lu‐Syuan , Chen Po‐Han , Lai Yi‐Fong , Chen Fang‐Chung
Published: August 2019

Indoor photovoltaics (IPVs) are attracting renewed interest because they can provide sustainable energy through the recycling of photon energy from household lighting facilities. Herein, the Shockley–Queisser model is used to calculate the upper limits of the power conversion efficiencies (PCEs) of perovskite solar cells (PeSCs) for two types of artificial light sources: fluorescent tubes (FTs) and white light–emitting diodes (WLEDs). An unusual zone is found in which the dependence of the PCEs on the bandgap (Eg) under illumination from the indoor lighting sources follows trends different from that under solar irradiation. In other words, IPVs exhibiting high performance under solar irradiation may not perform well under indoor lighting conditions. Furthermore, the ideal bandgap energy for harvesting photonic power from these indoor lighting sources is ≈1.9 eV—a value higher than that of common perovskite materials (e.g., for CH3NH3PbI3). Accordingly, Br− ions are added into the perovskite films to increase their values of Eg. A resulting PeSC featuring a wider bandgap exhibits PCEs of 25.94% and 25.12% under illumination from an FT and a WLED, respectively. Additionally, large‐area (4 cm2) devices are prepared for which the PCE reaches ≈18% under indoor lighting conditions.
Refilling Nitrogen to Oxygen Vacancies in Ultrafine Tungsten Oxide Clusters for Superior Lithium Storage
Authors: Cui Yanglansen , Xiao Kefeng , Bedford Nicholas M. , Lu Xinxin , Yun Jimmy , Amal Rose , Wang Da‐Wei
Published: August 2019

Morphological engineering of nanosized transitional metal oxides shows great promise for performance improvement, yet limited efforts have been attempted to engineer the atomic structure. Oxygen vacancy (VO) can boost charge transfer leading to enhanced performance; yet excessive VO may impair the conductivity. Herein, tungsten oxide is atomically tailored by incorporating nitrogen heteroatoms into the oxygen vacancies. The efficient nitrogen‐filling into the oxygen vacancies is evidenced by the electron paramagnetic resonance spectroscopy and X‐ray absorption spectroscopy. The coordinated N atoms play a crucial role in facilitating the charge transfer and maintaining efficient lithium‐ion diffusion. Consequently, the tungsten oxide with N‐filled oxygen vacancies exhibits superior lithium‐ion storage performance.
Sarcopenia discriminates poor prognosis in elderly patients following emergency surgery for perforation panperitonitis
Authors: Kubo Nobuhide , Kawanaka Hirohumi , Hiroshige Shoji , Tajiri Hirotada , Egashira Akinori , Takeuchi Hideya , Matsumoto Toshifumi , Oki Eiji , Yano Tokujiro
Published: August 2019

Aim

Sarcopenia has been reported as a prognostic predictor in various conditions; however, it has not been examined in patients with perforation panperitonitis.

Methods

A total of 103 consecutive patients with perforation panperitonitis who underwent emergency surgery from 2008 to 2016 were retrospectively evaluated. Skeletal muscle index (SMI) was measured as the cross‐sectional area (cm2) of skeletal muscle in the L3 region on computed tomography images normalized for height (cm2/m2). Sarcopenia was defined as an SMI of ≤43.75 and ≤41.10 cm2/m2 in men and women, respectively. The impact of sarcopenia on postoperative outcomes was investigated.

Results

Sarcopenia was present in 50 (48.5%) patients. Severe complications (Clavien‐Dindo grade ≥IIIb) and in‐hospital mortality were more frequently observed in patients with than without sarcopenia (28.0% vs 9.4%, P = .015) (20.0% vs 5.7%, P = .029) respectively. Multivariate analysis showed that age, sarcopenia, and renal dysfunction were independent risk factors for severe complications and in‐hospital mortality. The optimal cut‐off levels of age and SMI for predicting these were ≥79 years and SMI <38 cm2/m2, respectively. Among the patients aged ≥79 years, those with SMI <38 cm2/m2 had a severe complication rate of 71% and an in‐hospital mortality rate of 57%, whereas the rate of those with SMI ≥38 cm2/m2 was 22% (P = .011) and 11% (P = .008), respectively.

Conclusion

Sarcopenia is a predictive factor of severe complications and in‐hospital mortality following emergency surgery for perforation panperitonitis, especially in elderly patients. Estimation of sarcopenia may identify patients eligible or not eligible for emergency surgery among elderly patients.
Hydrogenation reactions catalyzed by colloidal palladium nanoparticles under flow regime
Authors: Reina Antonio , Favier Isabelle , Teuma Emmanuelle , Gómez Montserrat , Conte Annelyse , Pichon Laurent
Published: August 2019

A glycerol colloidal solution of palladium nanoparticles stabilized by PVP (PdPVP, mean diameter of 2.2 ± 0.8 × 10−9 m) was employed under flow conditions for hydrogenation reactions. After optimization, we selected the tube‐in‐tube flow reactor as the more suitable system for this catalytic process due to its ability to regulate the addition of hydrogen. PdPVP nanoparticles were synthesized and fully characterized ((HR)‐TEM, PXRD, EA, and ICP) both in glycerol solution and at solid state. The reduction of different substrates, including nitrobenzene, 4‐phenylbut‐3‐en‐2‐one, and isophorone, was achieved under relatively smooth conditions (5–7 × 105 Pa of H2) in short times (<600 s). Unfortunately, the reduction of 1‐dodecene was not possible due to the faster isomerization reaction. The optimal effusion of hydrogen in the colloidal phase together with the catalytic efficiency of this system is noteworthy.
Molecular Spin Crossover Materials: Review of the Lattice Dynamical Properties
Authors: Molnár Gábor , Mikolasek Mirko , Ridier Karl , Fahs Alaa , Nicolazzi William , Bousseksou Azzedine
Published: August 2019

The lattice dynamical aspects of the spin crossover phenomenon in molecular solids—displaying intricate couplings between the electronic spin state of the molecules and the lattice properties—are reviewed. Emphasis is on experimental and theoretical approaches giving access to the vibrational spectra and to key properties, such as the heat capacity, vibrational entropy and enthalpy, lattice rigidity, elastic constants, and elastic interactions. Recent results in relation to surface and finite size effects as well as with ultrafast out‐of‐equilibrium phenomena are also covered.
Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction
Authors: Zhang Zhan‐Ming , Xu Bing , Wu Lizuo , Wu Yuanqi , Qian Yanyan , Zhou Lujia , Liu Yu , Zhang Junliang
Published: August 2019

A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of a highly enantioselective intramolecular cyclization/cross‐coupling of olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.
Zinc Substitution of Cobalt in Vitamin B12: Zincobyric acid and Zincobalamin as Luminescent Structural B12‐Mimics
Authors: Kieninger Christoph , Baker Joseph A. , Podewitz Maren , Wurst Klaus , Jockusch Steffen , Lawrence Andrew D. , Deery Evelyne , Gruber Karl , Liedl Klaus R. , Warren Martin J. , Kräutler Bernhard
Published: August 2019

Replacing the central cobalt ion of vitamin B12 by other metals has been a long‐held aspiration within the B12‐field. Herein, we describe the synthesis from hydrogenobyric acid of zincobyric acid (Znby) and zincobalamin (Znbl), the Zn‐analogues of the natural cobalt‐corrins cobyric acid and vitamin B12, respectively. The solution structures of Znby and Znbl were studied by NMR‐spectroscopy. Single crystals of Znby were produced, providing the first X‐ray crystallographic structure of a zinc corrin. The structures of Znby and of computationally generated Znbl were found to resemble the corresponding CoII‐corrins, making such Zn‐corrins potentially useful for investigations of B12‐dependent processes. The singlet excited state of Znby had a short life‐time, limited by rapid intersystem crossing to the triplet state. Znby allowed the unprecedented observation of a corrin triplet (ET=190 kJ mol−1) and was found to be an excellent photo‐sensitizer for 1O2 (ΦΔ=0.70).
Ultrasensitive NOX Detection in Simulated Exhaled Air: Enhanced Sensing via Alumina Modification of In‐Situ Grown WO3 Nanoblocks
Authors: Alam Suhaib , Ansari Mohammad Shaad , Banik Avishek , Ali Rafat , Verma Sandeep , Qureshi Mohammad
Published: August 2019

Seedless growth of vertically aligned nanostructures, which can induce smoother transport and minimize Ohmic contact between substrate and semiconductor, can be fabricated by in situ growth utilizing modified hydrothermal methods. Such devices can be useful in designing non‐invasive ultrasensitive hand‐held sensors for diagnostic identification of volatile organic compounds (VOCs) in exhaled air, offering pain‐free and easier detection of long‐term diseases such as asthma. In the present work, WO3 nanoblocks, with a high surface area and porosity, have been grown directly over transparent conducting oxide to minimize Ohmic resistance, facilitating smoother electron transfer and enhanced current response. Further modification with porous alumina (γ‐Al2O3), by electrodeposition, resulted in the selective and ultrasensitive detection of NOX in simulated exhaled air. Crystal phase purity of as‐fabricated pristine as well modified samples is validated with X‐ray diffraction analysis. Morphological and microstructural analyses reveal the successful deposition of porous alumina over the surface of WO3. Improved surface area and porosity is presented by porous alumina in the modified WO3 device, suggesting more active sites for the gas molecules to get adsorbed and diffuse through the pores. Oxygen vacancies, which are detrimental in the transport phenomenon in the presented sensors, have been studied using X‐ray photoelectron spectroscopic (XPS) analysis. Gas sensing studies have been performed by fabricating chemiresistor devices based on bare WO3 and Al2O3‐modified WO3. The higher sensitivity for NOX gas in case of γ‐Al2O3‐modified WO3 based devices, as compared to bare WO3‐based devices, is attributed to the better surface area and charge transport kinetics. The presented device strategy offers crucial understanding in the design and development of non‐invasive, hand‐held devices for NO gas present in the human breath, with potential application in medical diagnostics.
Design and application of a KNX‐based home automation simulator for smart home system education
Authors: Toylan Mehmet Y. , Cetin Engin
Published: August 2019

Nowadays, automation systems have a wide use in buildings to make smart applications. Hence, many automation protocols such as 1‐wire, BACnet, C‐Bus, CC‐link, DALI, and KNX are developed. Among these protocols, the KNX protocol is preferred thanks to its some specifications such as easy and fast installation, user‐friendly software, and adaptation to the existing system. With increasing demand to construct KNX‐based smart home systems, developing the KNX‐based automation system simulator for the training of engineering students is required. A KNX simulator should be modular and user‐friendly. In addition, this simulator should have an expansion slot to use it together with different devices compatible with KNX protocol. In this study, a KNX simulator for engineering students training on smart home systems is designed and installed. The modules of simulator and KNX software programming tool ETS are explained. Besides, sample scenarios for engineering students to enhance and realize their projects are given.