bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Bipolar Blue AIEgens for High‐Performance Nondoped Blue OLEDs and Hybrid White OLEDs
Authors: Chen Bin , Liu Baiquan , Zeng Jiajie , Nie Han , Xiong Yi , Zou Jianhua , Ning Honglong , Wang Zhiming , Zhao Zujin , Tang Ben Zhong
Published: August 2018

Blue organic luminescent materials play a crucial role in full‐color display and white lighting but efficient ones meeting commercial demands are very rare. Herein, the design and synthesis of tailor‐made bipolar blue luminogens with an anthracene core and various functional groups are reported. The thermal stabilities, photophysical properties, electronic structures, electrochemical behaviors, carrier transport abilities, and electroluminescence performances are systematically investigated. The luminogen TPE‐TAPBI containing a tetraphenylethene moiety shows aggregation‐induced emission, while another luminogen TriPE‐TAPBI bearing a triphenylethene unit exhibits light aggregation‐caused quenching. In comparison with TriPE‐TAPBI, TPE‐TAPBI has stronger blue emission in neat film and functions more efficiently in nondoped organic light‐emitting diodes (OLEDs). High maxima current, power, and external quantum efficiencies of 7.21 cd A−1, 6.78 lm W−1, and 5.73%, respectively, are attained by the nondoped blue OLED of TPE‐TAPBI (CIEx,y = 0.15, 0.16). Moreover, efficient two‐color hybrid warm white OLEDs (CIEx,y = 0.457, 0.470) are achieved using TPE‐TAPBI neat film as the blue‐emitting component, which provide total current, power, external quantum efficiencies of up to 70.5 lm W−1, 76.0 cd A−1, and 28% at 1000 cd m−2, respectively. These blue and white OLEDs are among the most efficient devices with similar colors in the literature.
Shift of the Branching Point of the Side‐Chain in Naphthalenediimide (NDI)‐Based Polymer for Enhanced Electron Mobility and All‐Polymer Solar Cell Performance
Authors: You Hoseon , Kim Donguk , Cho Han‐Hee , Lee Changyeon , Chong Sanggyu , Ahn Nam Young , Seo Myungeun , Kim Jihan , Kim Felix Sunjoo , Kim Bumjoon J.
Published: August 2018

The branching point of the side‐chain of naphthalenediimide (NDI)‐based conjugated polymers is systematically controlled by incorporating four different side‐chains, i.e., 2‐hexyloctyl (P(NDI1‐T)), 3‐hexylnonyl (P(NDI2‐T)), 4‐hexyldecyl (P(NDI3‐T)), and 5‐hexylundecyl (P(NDI4‐T)). When the branching point is located farther away from the conjugated backbones, steric hindrance around the backbone is relaxed and the intermolecular interactions between the polymer chains become stronger, which promotes the formation of crystalline structures in thin film state. In particular, thermally annealed films of P(NDI3‐T) and P(NDI4‐T), which have branching points far away from the backbone, possess more‐developed bimodal structure along both the face‐on and edge‐on orientations. Consequently, the field‐effect electron mobilities of P(NDIm‐T) polymers are monotonically increased from 0.03 cm2 V−1 s−1 in P(NDI1‐T) to 0.22 cm2 V−1 s−1 in P(NDI4‐T), accompanied by reduced activation energy and contact resistance of the thin films. In addition, when the series of P(NDIm‐T) polymers is applied in all‐polymer solar cells (all‐PSCs) as electron acceptor, remarkably high‐power conversion efficiency of 7.1% is achieved along with enhanced current density in P(NDI3‐T)‐based all‐PSCs, which is mainly attributed to red‐shifted light absorption and enhanced electron‐transporting ability.
Carbon‐Based Nanomaterials for Cancer Therapy via Targeting Tumor Microenvironment
Authors: Saleem Jabran , Wang Liming , Chen Chunying
Published: August 2018

Cancer remains one of the major health problems all over the world and conventional therapeutic approaches have failed to attain an effective cure. Tumor microenvironments (TME) present a unique challenge in tumor therapy due to their complex structures and multiple components, which also serve as the soil for tumor growth, development, invasion, and migration. The complex TME includes immune cells, fibrous collagen structures, and tortuous blood vessels, in which conventional therapeutic approaches are rendered useless. State‐of‐the‐art nanotechnologies have potential to cope with the threats of malignant tumors. With unique physiochemical properties, carbon nanomaterials (CNMs), including graphene, fullerenes, carbon nanotubes, and carbon quantum dots, offer opportunities to resolve the hurdles, by targeting not only cancer cells but also the TME. This review summarizes the progress about CNM‐based cancer therapy strategies, which mainly focuses on both the treatment for cancer cells and TME‐targeted modulation. In the last, the challenges for TME‐based therapy via CNMs are discussed, which will be important in guiding current basic research to clinical translation in the future.
Self‐Assembled Nanomedicines for Anticancer and Antibacterial Applications
Authors: Zhou Lingyun , Qiu Tian , Lv Fengting , Liu Libing , Ying Jianming , Wang Shu
Published: August 2018

Self‐assembly strategies have been widely applied in the nanomedicine field, which provide a convenient approach for building various structures for delivery carriers. When cooperating with biomolecules, self‐assembly systems have significant influence on the cell activity and life process and could be used for regulating nanodrug activity. In this review, self‐assembled nanomedicines are introduced, including materials, encapsulation, and releasing strategies, where self‐assembly strategies are involved. Furthermore, as a promising and emerging area for nanomedicine, in situ self‐assembly of anticancer drugs and supramolecular antibiotic switches is also discussed about how to regulate drug activity. Selective pericellular assembly can block mass transformation of cancer cells inducing cell apoptosis, and the intracellular assembly can either cause cell death or effectively avoid drug elimination from cytosol of cancer cells because of the assembly‐induced retention (AIR) effect. Host–guest interactions of drug and competitive molecules offer reversible regulations of antibiotic activity, which can reduce drug‐resistance and inhibit the generation of drug‐resistant bacteria. Finally, the challenges and development trend in the field are discussed.
State‐of‐the‐Art and Future Prospects for Atomically Thin Membranes from 2D Materials
Authors: Prozorovska Liudmyla , Kidambi Piran R.
Published: August 2018

Atomically thin 2D materials, such as graphene, hexagonal boron‐nitride, and others, offer new possibilities for ultrathin barrier and membrane applications. While the impermeability of pristine 2D materials to gas molecules, such as He, allows the realization of the thinnest physical barrier, nanoscale vacancy defects in the 2D material lattice manifest as nanopores in an atomically thin membrane. Such nanoporous atomically thin membranes (NATMs) present potential for enabling ultrahigh permeance and selectivity in a wide range of novel separation processes. Herein, the transport properties observed in NATMs are described and recent experimental progress achieved in their fabrication is summarized. Some of the challenges in NATM scale‐up for practical applications are highlighted and several opportunities are identified, including the possibility of blending traditional membrane‐processing approaches. Finally, a technological roadmap is presented with a contextual discussion for NATMs to progress from research to applications.
Autonomous Flexible Sensors for Health Monitoring
Authors: Huynh Tan‐Phat , Haick Hossam
Published: August 2018

A concise, although admittedly non‐exhaustive, didactic summary is given of some of the main concepts and approaches related to recent advances and developments to enable autonomous detection and monitoring of the likelihood or existence of a health risk state in continuous and real‐time modes. To give a comprehensive statement, different aspects of these advanced materials and related devices are presented and discussed, such as: flexible sensors used for non‐invasive detection of health‐related physiological markers; self‐powered materials to enable extended usage periods by harvesting energy from body movement and temperature; and self‐healing properties of the materials used on the wearable devices to enable extended usage periods if scratched or cut. The linkage of these advanced materials and technologies together is particularly specified. Some of the strong and weak points in the development of each wearable material/device are clearly highlighted and criticized. Several ideas regarding further improvement of skin‐based wearable devices are also discussed.
Logic Computing with Stateful Neural Networks of Resistive Switches
Authors: Sun Zhong , Ambrosi Elia , Bricalli Alessandro , Ielmini Daniele
Published: August 2018

Brain‐inspired neural networks can process information with high efficiency, thus providing a powerful tool for pattern recognition and other artificial intelligent tasks. By adopting binary inputs/outputs, neural networks can be used to perform Boolean logic operations, thus potentially surpassing complementary metal–oxide–semiconductor logic in terms of area efficiency, execution time, and computing parallelism. Here, the concept of stateful neural networks consisting of resistive switches, which can perform all logic functions with the same network topology, is introduced. The neural network relies on physical computing according to Ohm's law, Kirchhoff 's law, and the ionic migration within an output switch serving as the highly nonlinear activation function. The input and output are nonvolatile resistance states of the devices, thus enabling stateful and cascadable logic operations. Applied voltages provide the synaptic weights, which enable the convenient reconfiguration of the same circuit to serve various logic functions. The neural network can solve all two‐input logic operations with just one step, except for the exclusive‐OR (XOR) needing two sequential steps. 1‐bit full adder operation is shown to take place with just two steps and five resistive switches, thus highlighting the high efficiencies of space, time, and energy of logic computing with the stateful neural network.
Highly Efficient Visible Light Photocatalytic Activities in Self‐Assembled Metastable TiO2/Bi4MoO9 Heterojunctions
Authors: Fang Guoli , Liu Jia , Yan Xianghui , Wang Danyang , Israr Jahanzaib , Xue Tong
Published: August 2018

Metastable TiO2/Bi4MoO9 heterojunctions are synthesized using a hydrothermal method. TiO2 nanoparticles, which are used as templates in the hydrothermal process, can induce the heterogeneous nucleation and 1D preferential growth of Bi4MoO9 to form TiO2/Bi4MoO9 heterojunctions. The TiO2/Bi4MoO9 heterojunctions exhibit very efficient visible‐light photocatalytic activity, which is much higher than those of TiO2 nanoparticles, Bi4MoO9 microcubes, and TiO2/Bi2MoO6 composites. This could be mainly ascribed to the synergistic effects of the band structure matching and the unique microstructure between TiO2 nanoparticles and Bi4MoO9 nanobelts in the heterojunctions. The Bi4MoO9 nanobelts with ≈150 nm in width promote the production of photogenerated electron–hole pairs due to its narrow bandgap. The TiO2 nanoparticles embedded into Bi4MoO9 nanobelts still remain small size, large specific surface area, and high crystallinity. These not only facilitate the transfer of photogenerated holes from Bi4MoO9 nanobelts to TiO2 nanoparticles, but also improve the holes capture rate on the surface of the heterojunctions.
Organized Community Activity Participation and the Dynamic Roles of Neighborhood Violence and Gender among Latino Adolescents
Authors: Camacho‐Thompson Daisy E. , Vargas Robert
Published: August 2018

Relative to their peers, Latino youth are underinvolved in organized community activities (e.g., Boys and Girls Club), and their experiences lack examination. This study employed a neighborhood case‐study approach to examine the experiences of Latino youth in a neighborhood with high levels of violence and their participation in organized community activities. Employing a cluster sampling design (Lohr, Sampling: Design and analysis. Pacific Grove, CA: Nelson Education, 2009), we used quantitative, spatial, and qualitative data to understand adolescents’ participation in organized community activities. Furthermore, to understand how adolescents from the same neighborhood may experience violence differently we examined gender differences. Those who participated in organized community activities witnessed more violence, regardless of gender. General violence (e.g., robberies, shootings) was dispersed throughout the neighborhood, but gender‐specific violence was concentrated along the main street of the neighborhood. In qualitative interviews, adolescents reported this concentration of violence a deterrent to their participation: sexual harassment for girls and gang intimidation for boys. Our findings highlight the unique experiences of youth in violent neighborhoods and the importance of examining differential constraints for those within the same neighborhood.
Glasdegib in combination with cytarabine and daunorubicin in patients with AML or high‐risk MDS: Phase 2 study results
Authors: Cortes Jorge E. , Douglas Smith B. , Wang Eunice S. , Merchant Akil , Oehler Vivian G. , Arellano Martha , DeAngelo Daniel J. , Pollyea Daniel A. , Sekeres Mikkael A. , Robak Tadeusz , Ma Weidong Wendy , Zeremski Mirjana , Naveed Shaik M. , Douglas Laird A. , O'Connell Ashleigh , Chan Geoffrey , Schroeder Mark A.
Published: August 2018

Glasdegib is a Hedgehog pathway inhibitor. This ongoing, open‐label, phase 2 study (NCT01546038) evaluated glasdegib plus cytarabine/daunorubicin in patients with untreated acute myeloid leukemia (AML) or high‐risk myelodysplastic syndromes (MDS). Patients received glasdegib 100 mg orally, once daily in continuous 28‐day cycles from day −3, with intravenous cytarabine 100 mg/m2 on days 1‐7 and daunorubicin 60 mg/m2 on days 1‐3. Patients in remission then received consolidation therapy (2‐4 cycles of cytarabine 1 g/m2 twice daily on days 1, 3, 5 of each cycle), followed by maintenance glasdegib (maximum 6 cycles). Primary endpoint was complete remission (CR) in patients aged ≥55 years. Secondary endpoints included overall survival (OS), safety and outcome by mutational status. Patients had a median (range) age of 64.0 (27‐75) years, 60.0% were male, and 84.5% were white. In 69 evaluable patients, 46.4% (80% confidence interval [CI]: 38.7‐54.1) achieved investigator‐reported CR. Among patients ≥55 years old (n = 60), 40.0% (80% CI 31.9‐48.1) achieved CR. Among all 69 patients, median OS was 14.9 (80% CI 13.4‐19.3) months, with 12‐month survival probability 66.6% (80% CI 58.5‐73.4). The most common treatment‐related adverse events (≥50% patients) were diarrhea and nausea. There were no significant associations between mutational status (12 genes) and clinical response, suggesting potential benefit across diverse molecular profiles. Glasdegib plus cytarabine/daunorubicin was well tolerated and associated with clinical activity in patients with untreated AML or high‐risk MDS. A randomized phase 3 trial of glasdegib in combination with chemotherapy (7 + 3 schedule) is ongoing.
Dual diagnoses in 152 patients with Turner syndrome: Knowledge of the second condition may lead to modification of treatment and/or surveillance
Authors: Jones Kelly L. , McNamara Erin A. , Longoni Mauro , Miller Danny E. , Rohanizadegan Mersedeh , Newman Laura A. , Hayes Frances , Levitsky Lynne L. , Herrington Betty L. , Lin Angela E.
Published: August 2018

Turner syndrome is a sex chromosome abnormality in which a female has a single X chromosome or structurally deficient second sex chromosome. The phenotypic spectrum is broad, and atypical features prompt discussion of whether the known features of Turner syndrome should be further expanded. With the advent of clinical whole exome sequencing, there has been increased realization that some patients with genetic disorders carry a second genetic disorder, leading us to hypothesize that a “dual diagnosis” may be more common than suspected for Turner syndrome. We report five new patients with Turner syndrome and a co‐occurring genetic disorder including one patient with Li‐Fraumeni syndrome, Li‐Fraumeni and Noonan syndrome, mosaic trisomy 8, pathogenic variant in RERE, and blepharophimosis‐ptosis‐epicanthanus inversus syndrome. We also undertook an extensive literature review of 147 reports of patients with Turner syndrome and a second genetic condition. A total of 47 patients (31%) had trisomy 21, followed by 36 patients (24%) had one of 11 X‐linked disorders. Notably, 80% of the 147 reported patients with a dual diagnosis had mosaicism for Turner syndrome, approximately twice the frequency in the general Turner syndrome population. This article demonstrates the potential for co‐occurring syndromes in patients with Turner syndrome, prompting us to recommend a search for an additional genetic disorder in Turner patients with unusual features. Knowledge of the second condition may lead to modification of treatment and/or surveillance. We anticipate that increased awareness and improved diagnostic technologies will lead to the identification of more cases of Turner syndrome with a co‐occurring genetic syndrome.
Immunoadjuvant therapy in sepsis: novel strategies for immunosuppressive sepsis coming down the pike
Authors: Watanabe Eizo , Thampy Lukose K. , Hotchkiss Richard S.
Published: August 2018

Recent efforts have focused on immunoadjuvant therapies for sepsis. The host inflammatory response consequent to initial exposure to pathogens is often followed by anti‐inflammatory forces, resulting in increased morbidity and mortality in such critically ill patients. In the subacute stage of sepsis, apoptosis (type I programmed cell death) and subsequently autophagy (type II programmed cell death) have been attracting recent research interest. Although many patients may die during the initial cytokine storm, those who survive this phase might acquire defining characteristics of profound immunosuppression, including failure to clear the primary infection, development of secondary opportunistic infections, and reactivation of latent viruses. Both types of cell death are currently thought to be associated with this subacute immunosuppressive phase of sepsis, and acceleration of autophagy might alleviate immunosuppression through regulation of apoptosis of key immune effector cells. Programmed cell death 1 (PD‐1) and its corresponding ligand play a major pathological role in immunosuppression not only in cancer but also in sepsis. Positive costimulatory pathways in T cells, such as CD28 signaling, permit the effector T cell to expand, persist, and effectively clear antigen. However, PD‐1 is a negative costimulatory pathway on T cells that broadly enhances immunosuppressive signals across the innate and adaptive immune system. To counter this immunosuppression in sepsis, checkpoint blockade has garnered attention in an area of clinical research. In this review, we introduce some approaches of immunotherapy using anti‐PD‐1 antibody in infectious diseases and share our future perspectives.
The Transition‐Metal‐Like Behavior of B2(NHC)2 in the Activation of CO: HOMO–LUMO Swap Without Photoinduction
Authors: Zhang Huaiyu , Cao Zexing , Wu Wei , Mo Yirong
Published: August 2018

It is a current trend to explore multi‐bonded and unsaturated main group compounds that can interact with small molecules, in order to find non‐metal catalysts. Notably, Braunschweig et al. found that diboryne stabilized by N‐heterocyclic carbenes (NHCs) can bind and activate CO. Here we explore the bonding nature of B2(NHC)2 and its activation mechanism for CO from a novel theoretical perspective. While the ground state of B2 is of a single bond, the approach of NHCs excites B2 to its third excited state of a triple bond with two significant σ‐holes at the two ends. The subsequent electrostatic attraction drives the formation of B2(NHC)2. However, only one of the two π bonds (HOMOs) of B2(NHC)2 fits to one of the degenerate LUMOs of CO. Interestingly, the strong steric repulsion between CO and B2(NHC)2 leads to the HOMO–LUMO swap in the latter. Subsequently, both HOMO and HOMO−1 of B2(NHC)2 can effectively interact with the two π* anti‐bonding orbitals (LUMO and LUMO+1) of CO, resulting in substantial electron back‐donation and the ultimate activation of CO.
Alkoxyl Radicals Generated under Photoredox Catalysis: A Strategy for anti‐Markovnikov Alkoxylation Reactions
Authors: Barthelemy Anne‐Laure , Tuccio Béatrice , Magnier Emmanuel , Dagousset Guillaume
Published: August 2018

Reported herein is a novel photoredox‐catalyzed approach for ether synthesis and it involves alkoxyl radicals generated from N‐alkoxypyridinium salts. A wide range of alkenes are smoothly difunctionalized in an anti‐Markovnikov fashion, affording various functionalized alkyl alkyl ethers. Notably, this mild process tolerates a number of functional groups and is efficiently carried out under both batch and flow conditions. Importantly, electron paramagnetic resonance (EPR) experiments by spin trapping were carried out to characterize the radical intermediates involved in this radical/cationic process.
Silver‐Promoted Oxidative Benzylic C−H Trifluoromethoxylation
Authors: Yang Haodong , Wang Feng , Jiang Xiaohuan , Zhou Yu , Xu Xiufang , Tang Pingping
Published: August 2018

A silver‐promoted oxidative benzylic C−H trifluoromethoxylation has been reported for the first time. With trifluoromethyl arylsulfonate as the trifluoromethoxylation reagent, various arenes, having diverse functional groups, undergo trifluoromethoxylation of their benzylic C−H bonds to form trifluoromethyl ethers under mild reaction conditions. In addition, the trifluoromethoxylation and the fluorination of methyl groups of electron‐rich arenes have been achieved to prepare α‐fluorobenzyl trifluoromethyl ethers in one step.
Einzelnanopartikel‐Strichkodierung von Zellen mittels durchstimmbarem FRET von Lanthanoiden auf Quantenpunkte
Authors: Chen Chi , Ao Lijiao , Wu Yu‐Tang , Cifliku Vjona , Cardoso Dos Santos Marcelina , Bourrier Emmanuel , Delbianco Martina , Parker David , Zwier Jurriaan M. , Huang Liang , Hildebrandt Niko
Published: August 2018

Fluoreszenzstrichkodierung mittels Nanopartikeln bietet viele Vorteile für die Multiparameter‐Mikroskopie. Es ist jedoch extrem schwierig, verschiedene konzentrationsunabhängige Codes zu erstellen, ohne verschiedene Nanopartikel zu mischen und Anregung und Emission einer einzelnen Wellenlänge für die zelluläre Multiplex‐Bildgebung zu verwenden. Hier berichten wir über die Entwicklung von Quantenpunkten (quantum dots: QDs) mit zwei unterschiedlichen SiO2‐Schalenstärken (6 und 12 nm), die mit zwei verschiedenen Lanthanoidkomplexen (Tb und Eu) beschichtet sind. FRET von Tb‐ oder Eu‐Donoren auf QD‐Akzeptoren führte zu vier unterschiedlichen Photolumineszenz(PL)‐Abklingkurven, die durch einfache zeitgetaktete (time‐gated: TG) PL‐Intensitätsdetektion in drei individuellen temporalen Detektionsfenstern kodiert wurden. Die wohldefinierten Einzelnanopartikel‐Codes wurden für die Lebendzellen‐Mikroskopie und die Unterscheidung von vier verschiedenen Zellen in einem einzigen Sichtfeld mittels einer Messung verwendet. Diese Einzelfarben‐Strichkodierungsstrategie eröffnet neue Möglichkeiten für die Multiplexmarkierung und Verfolgung von Zellen.
Cross‐Linked Aptamer–Lipid Micelles for Excellent Stability and Specificity in Target‐Cell Recognition
Authors: Li Xiaowei , Figg C. Adrian , Wang Ruowen , Jiang Ying , Lyu Yifan , Sun Hao , Liu Yuan , Wang Yanyue , Teng I‐Ting , Hou Weijia , Cai Ren , Cui Cheng , Li Long , Pan Xiaoshu , Sumerlin Brent S. , Tan Weihong
Published: August 2018

The specific binding ability of DNA–lipid micelles (DLMs) can be increased by the introduction of an aptamer. However, supramolecular micellar structures based on self‐assemblies of amphiphilic DLMs are expected to demonstrate low stability when interacting with cell membranes under certain conditions, which could lead to a reduction in selectivity for targeting cancer cells. We herein report a straightforward cross‐linking strategy that relies on a methacrylamide branch to link aptamer and lipid segments. By an efficient photoinduced polymerization process, covalently linked aptamer–lipid units help stabilize the micelle structure and enhance aptamer probe stability, further improving the targeting ability of the resulting nanoassembly. Besides the development of a facile cross‐linking method, this study clarifies the relationship between aptamer–lipid concentration and the corresponding binding ability.
A Green BODIPY‐Based, Super‐Fluorogenic, Protein‐Specific Labelling Agent
Authors: Chen Yingche , Tsao Kelvin , Acton Sydney L. , Keillor Jeffrey W.
Published: August 2018

We report the development of YC23, a novel green BODIPY‐based dimaleimide derivative that undergoes a fluorogenic addition reaction (FlARe) with a genetically encodable peptide tag (dC10α) that can be fused to a protein of interest (POI). We also demonstrate the application of this reaction for the fluorogenic labelling of a specific POI in bacterial lysate and in living mammalian cells.
Capturing the Genesis of an Active Fischer–Tropsch Synthesis Catalyst with Operando X‐ray Nanospectroscopy
Authors: van Ravenhorst Ilse K. , Vogt Charlotte , Oosterbeek Heiko , Bossers Koen W. , Moya‐Cancino José G. , van Bavel Alexander P. , van der Eerden Ad M. J. , Vine David , de Groot Frank M. F. , Meirer Florian , Weckhuysen Bert M.
Published: August 2018

A state‐of‐the‐art operando spectroscopic technique is applied to Co/TiO2 catalysts, which account for nearly half of the world's transportation fuels produced by Fischer–Tropsch catalysis. This allows determination of, at a spatial resolution of approximately 50 nm, the interdependence of formed hydrocarbon species in the inorganic catalyst. Observed trends show intra‐ and interparticular heterogeneities previously believed not to occur in particles under 200 μm. These heterogeneities are strongly dependent on changes in H2/CO ratio, but also on changes thereby induced on the Co and Ti valence states. We have captured the genesis of an active FTS particle over its propagation to steady‐state operation, in which microgradients lead to the gradual saturation of the Co/TiO2 catalyst surface with long chain hydrocarbons (i.e., organic film formation).
The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts
Authors: Mitchell Sharon , Vorobyeva Evgeniya , Pérez‐Ramírez Javier
Published: August 2018

Single‐atom heterogeneous catalysts (SACs) attached to carefully chosen hosts are attracting considerable interest; principally because they offer maximum utilization per metal atom and are usually readily recyclable. However, diminution of the atomic population of nanoparticles or nanoclusters to single atoms can significantly alter reactivity because of the consequent changes in the active‐site structure. By examining various diverse applications, we ascertain whether the performance of SACs is enhanced or suppressed. We also note that SACs generally display unique kinds of catalytic cycles. The choice of host is crucial since it influences both the electronic and steric environment of the metal center. Moreover, it may function as a cocatalyst. All these aspects impact upon the design of new SACs, which exhibit similarities to hetero‐ and homogeneous predecessors. Additionally, SACs offer a viable replacement of soluble metal complexes in processes that remain difficult to heterogenize.
Sensing Picomolar Concentrations of RNA Using Switchable Plasmonic Chirality
Authors: Funck Timon , Nicoli Francesca , Kuzyk Anton , Liedl Tim
Published: August 2018

Detecting small sequences of RNA in biological samples such as microRNA or viral RNA demands highly sensitive and specific methods. Here, a reconfigurable DNA origami template has been used where a chiral arrangement of gold nanorods on the structure can lead to the generation of strong circular dichroism (CD). Switching of the cross‐like DNA structure is achieved by the addition of nucleic acid sequences, which arrests the structure in one of the possible chiral states by specific molecular recognition. A specific sequence can thus be detected through the resulting changes in the plasmonic CD spectrum. We show the sensitive and selective detection of a target RNA sequence from the hepatitis C virus genome. The RNA binds to a complementary sequence that is part of the lock mechanism, which leads to the formation of a defined state of the plasmonic system with a distinct optical response. With this approach, we were able to detect this specific RNA sequence at concentrations as low as 100 pm.
Enantioselective Palladium‐Catalyzed [3+2] Cycloaddition of Trimethylenemethane and Fluorinated Ketones
Authors: Trost Barry M. , Mata Guillaume
Published: August 2018

A nitrile‐substituted trimethylenemethane (TMM) donor undergoes palladium‐catalyzed [3+2] cycloadditions with fluorinated ketones to generate tetrasubstituted trifluoromethylated centers in high enantioselectivity under mild conditions. The generation of the palladium–TMM complex was achieved by a self‐deprotonation strategy, which shows remarkable improvements in regiocontrol, efficiency, and atom economy of asymmetric [3+2] cycloadditions. Moreover, the versatility of the nitrile group provides direct access to a variety of synthetically useful intermediates, including amides, aldehydes, and esters. The developed reaction conditions allow for the synthesis of a wide variety of aromatic, heteroaromatic, and aliphatic fluorinated dihydrofurans in excellent regio‐ and enantioselectivities.
Ring‐Opening Copolymerization of Maleic Anhydride with Functional Epoxides: Poly(propylene fumarate) Analogues Capable of Post‐Polymerization Modification
Authors: Chen Yusheng , Wilson James A. , Petersen Shannon R. , Luong Derek , Sallam Sahar , Mao Jialin , Wesdemiotis Chrys , Becker Matthew L.
Published: August 2018

Three functional epoxides were copolymerized with maleic anhydride to yield degradable poly(propylene fumarate) analogues. The polymers were modified post‐polymerization and post‐printing with either click‐type addition reactions or UV deprotection to either attach bioactive species or increase the hydrophilicity. Successful dye attachment, induced wettability, and improved cell spreading show the viability of these analogues in biomaterials applications.
Single‐Nanoparticle Cell Barcoding by Tunable FRET from Lanthanides to Quantum Dots
Authors: Chen Chi , Ao Lijiao , Wu Yu‐Tang , Cifliku Vjona , Cardoso Dos Santos Marcelina , Bourrier Emmanuel , Delbianco Martina , Parker David , Zwier Jurriaan M. , Huang Liang , Hildebrandt Niko
Published: August 2018

Fluorescence barcoding based on nanoparticles provides many advantages for multiparameter imaging. However, creating different concentration‐independent codes without mixing various nanoparticles and by using single‐wavelength excitation and emission for multiplexed cellular imaging is extremely challenging. Herein, we report the development of quantum dots (QDs) with two different SiO2 shell thicknesses (6 and 12 nm) that are coated with two different lanthanide complexes (Tb and Eu). FRET from the Tb or Eu donors to the QD acceptors resulted in four distinct photoluminescence (PL) decays, which were encoded by simple time‐gated (TG) PL intensity detection in three individual temporal detection windows. The well‐defined single‐nanoparticle codes were used for live cell imaging and a one‐measurement distinction of four different cells in a single field of view. This single‐color barcoding strategy opens new opportunities for multiplexed labeling and tracking of cells.
α‐ZrP/Uracil/Cu2+ nanoparticles as an efficient catalyst in the Morita‐Baylis‐Hillman reaction
Authors: Hajipour Abdol R. , Zakery Saedeh
Published: August 2018

A facile synthesis of uracil‐Cu2+ nanoparticles immobilized on alpha‐zirconium hydrogen phosphate (α‐ZrP), abbreviated as α‐ZrP/Uracil/Cu2+, was presented. This compound was synthesized by the thermal method and used as a reusable catalyst for the Morita‐Baylis‐Hillman reaction without any additives. First, (3‐ iodopropyl) trimethoxysilane as a linker is reacted with α‐ZrP support to give the α‐ZrP/IPTMOS. Addition of uracil and then the addition of copper (II) acetate to α‐ZrP/IPTMOS results in the production of selected catalyst. The Morita‐Baylis‐Hillman reaction catalyzed by α‐ZrP/Uracil/Cu2+ demonstrated high product yield, short reaction time and a straightforward work‐up. The catalyst with enough outside surface was easily recovered using centrifugation and reused five times without a significant reduction in its activity.
Fabrication and properties of PVDF and PVDF‐HFP microfiltration membranes
Authors: Wang Xinya , Xiao Changfa , Liu Hailiang , Huang Qinglin , Fu Hao
Published: August 2018

Poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride)‐co‐hexafluoropropylene (PVDF‐HFP) were used to fabricate porous microfiltration membranes via a thermally induced phase separation (TIPS) method, and dibutyl phthalate (DBP) was used as diluent. The effects of polymer concentration on structure and performance were studied in detail. In addition, the effect of incorporation of hexafluoropropylene (HFP) groups on the membrane was also investigated. The formation mechanism was proposed with the assistance of a phase diagram. The results showed that the incorporation of HFP groups resulted in a lower crystallization temperature (Tc) of the polymer/DBP system. In addition, the porosity, pure water flux, and ink solution flux decreased with increasing polymer concentration. In contrast, the water contact angle, ink rejection ratio, and mechanical properties had an increasing tendency. When the polymer concentration was 30 wt %, the obtained membrane was most suitable for microfiltration. Furthermore, the incorporation of HFP groups improved the properties of the obtained membrane, including better hydrophobicity, mechanical properties, antifouling property, and chemical resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46711.
Tackling slip effects in the nonlinear flow properties of gellan fluid gels
Authors: García Mª Carmen , Sánchez Sergio , Trujillo‐Cayado Luis A. , Muñoz José , Alfaro Mª Carmen
Published: August 2018

Gellan gum is a biopolymer widely used in the food, pharmaceutical, chemical, and agrochemical fields. Its ability to form a strong gel makes it possible to produce fluid gels. These materials present an apparent yield stress, but its value could be influenced by the wall‐slip effect when performing the rheological measurements by which it is determined. In this work, the influence of the measuring surface and gap on flow behavior was first determined. The tests revealed the need to use geometries with rough surfaces, although the sample thickness using a parallel plate has no influence. Subsequently, the value of yield stress was obtained by means of creep tests (found to be 4.3 Pa), and, finally, the effect of wall slip on the dynamic viscoelastic behavior was assessed. There was an influence on the extension of the linear viscoelastic region, but not on the viscoelastic functions of the mechanical spectra. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46900.
Influence of Disease Activity in Rheumatoid Arthritis on Radiographic Progression of Concomitant Interphalangeal Joint Osteoarthritis
Authors: Lechtenboehmer Christian A. , Jaeger Veronika K. , Kyburz Diego , Walker Ulrich A. , Hügle Thomas
Published: August 2018

Objective

Distal interphalangeal (DIP) joints are commonly considered to be unaffected by rheumatoid arthritis (RA). Despite synovitis and bone marrow edema being associated with radiographic progression in hand osteoarthritis (OA) and hand RA, radiographic courses differ substantially. This study was undertaken to analyze incidence and progression of radiographically evident DIP joint OA in RA patients, in relation to RA activity and patient characteristics.

Methods

In sequential radiographs of 1,988 RA patients in the Swiss Clinical Quality Management in Rheumatic Diseases registry, we evaluated and scored 15,904 DIP joints. Scoring was based on the presence of central erosions and subchondral sclerosis and on the severity of osteophytes and joint space narrowing, according to the modified Kellgren/Lawrence (K/L) grade. The presence of DIP joint OA was defined as ≥1 joint with a K/L grade of ≥2, and progression was defined as an increase in a summed K/L grade. Adjusted odds ratios (ORs) and 95% confidence intervals (95% CIs) were calculated.

Results

The median follow‐up time was 4.5 years (interquartile range 3.1–7.0), and the mean ± SD age was 56.1 ± 11.1 years. DIP joint OA was present in 60% of patients at baseline. Higher mean age (OR 1.09 [95% CI 1.08–1.10]), female sex (OR 1.37 [95% CI 1.08–1.74]), and higher mean body mass index (OR 1.03 [95% CI 1.00–1.06]) were associated with the presence of DIP joint OA, but neither the presence of anti–citrullinated protein antibodies (ACPAs) (OR 0.72 [95% CI 0.50–1.03]) nor the presence of rheumatoid factor (OR 1.01 [95% CI 0.74–1.38]) were associated with it. Disease Activity Score using the erythrocyte sedimentation rate and metacarpophalangeal (MCP) joint erosions were not associated with DIP joint OA progression. RA disease duration had no relevant effect size associated with DIP joint OA progression (OR 0.97 [95% CI 0.96–0.99]).

Conclusion

Known risk factors for DIP joint OA were replicated in patients with RA. The observation that RA activity, the presence of ACPA, and MCP joint erosions were not associated with the prevalence or progression of DIP joint OA indicates that there are distinct roles of inflammation in the pathogenesis of RA and DIP joint OA.
Blinded and unblinded sample size reestimation in crossover trials balanced for period
Authors: Grayling Michael J. , Mander Adrian P. , Wason James M. S.
Published: August 2018

The determination of the sample size required by a crossover trial typically depends on the specification of one or more variance components. Uncertainty about the value of these parameters at the design stage means that there is often a risk a trial may be under‐ or overpowered. For many study designs, this problem has been addressed by considering adaptive design methodology that allows for the re‐estimation of the required sample size during a trial. Here, we propose and compare several approaches for this in multitreatment crossover trials. Specifically, regulators favor reestimation procedures to maintain the blinding of the treatment allocations. We therefore develop blinded estimators for the within and between person variances, following simple or block randomization. We demonstrate that, provided an equal number of patients are allocated to sequences that are balanced for period, the proposed estimators following block randomization are unbiased. We further provide a formula for the bias of the estimators following simple randomization. The performance of these procedures, along with that of an unblinded approach, is then examined utilizing three motivating examples, including one based on a recently completed four‐treatment four‐period crossover trial. Simulation results show that the performance of the proposed blinded procedures is in many cases similar to that of the unblinded approach, and thus they are an attractive alternative.
Mechanoluminescence of Ce/Tb inorganic salts in methane–acetylene mixtures with inert gases
Authors: Tukhbatullin Adis A. , Sharipov Glyus L. , Galina Aygul A.
Published: August 2018

The mechanoluminescence of cerium (Ce) and terbium (Tb) lanthanide salts is studied in hydrocarbon [methane (CH4) and acetylene (C2H2)] and inert [helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe)] gaseous mixtures. The lines of *N2, *Ln3+, inert gases, *CH, and *C2 radicals resulted from the mechanochemical decomposition of CH4 and C2H2 are observed in the emission spectrum. The luminescence intensity of the inert gases decreases with the hydrocarbon gas concentration in the mixture. The intensities of the *CH or *C2 bands remains almost unchanged within 15–100 vol% of CH4 or C2H2 in the mixture. When the concentration of CH4 or C2H2 is lower than 15%, the intensities of the CH or C2 bands increase achieving their maxima at 0.5–3% of the hydrocarbon. This is probably due to the optimal compositions of the mixtures with the most efficient generation of electrical discharges responsible for mechanoluminescence.
Progression of continuous downstream processing of monoclonal antibodies: Current trends and challenges
Authors: Somasundaram Balaji , Pleitt Kristina , Shave Evan , Baker Kym , Lua Linda H. L.
Published: August 2018

Rapid advances in intensifying upstream processes for biologics production have left downstream processing as a bottleneck in the manufacturing scheme. Biomanufacturers are pursuing continuous downstream process development to increase efficiency and flexibility, reduce footprint and cost of goods, and improve product consistency and quality. Even after successful laboratory trials, the implementation of a continuous process at manufacturing scale is not easy to achieve. This paper reviews specific challenges in converting each downstream unit operation to a continuous mode. Key elements of developing practical strategies for overcoming these challenges are detailed. These include equipment valve complexity, favorable column aspect ratio, protein‐A resin selection, quantitative assessment of chromatogram peak size and shape, holistic process characterization approach, and a customized process economic evaluation. Overall, this study provides a comprehensive review of current trends and the path forward for implementing continuous downstream processing at the manufacturing scale.
Timing of carotid intervention
Authors: Meershoek A J A , de Borst G J
Published: August 2018

Flimsy evidence
Development of a method for the determination of hydromorphone in plasma by LC–MS
Authors: Cox Sherry , Bergman Joan , Hawkins Shawna , Sladky Kurt
Published: August 2018

A simple high‐performance liquid chromatography method for the determination of hydromorphone in small volume plasma has been developed. Following solid‐phase extraction using Oasis HLB cartridges, samples were separated by reverse‐phase high‐performance liquid chromatography on an Atlantis T3 4.6 × 150 mm column (3.0 μm) and quantified using mass spectrometry. The mobile phase was a mixture of water with 0.1% formic acid and acetonitrile with 0.1% formic acid (91:9). The standard curve ranged from 1 to 500 ng/mL. Intra‐ and Inter‐assay variability for hydromorphone was <10%, and the average recovery was >90%. The LLOQ was 1 ng/mL. This method was successfully applied to the analysis of hydromorphone samples at this institution. This method could be useful to those investigators dealing with small sample volumes, particularly when conducting pharmacokinetic studies that require multiple sampling from the same animal.
Applications of decellularized extracellular matrix in bone and cartilage tissue engineering
Authors: Kim Yu Seon , Majid Marjan , Melchiorri Anthony J. , Mikos Antonios G.
Published: August 2018

Regenerative therapies for bone and cartilage injuries are currently unable to replicate the complex microenvironment of native tissue. There are many tissue engineering approaches attempting to address this issue through the use of synthetic materials. Although synthetic materials can be modified to simulate the mechanical and biochemical properties of the cell microenvironment, they do not mimic in full the multitude of interactions that take place within tissue. Decellularized extracellular matrix (dECM) has been established as a biomaterial that preserves a tissue's native environment, promotes cell proliferation, and provides cues for cell differentiation. The potential of dECM as a therapeutic agent is rising, but there are many limitations of dECM restricting its use. This review discusses the recent progress in the utilization of bone and cartilage dECM through applications as scaffolds, particles, and supplementary factors in bone and cartilage tissue engineering.
The efficacy of Stereotactic body radiation therapy and the impact of systemic treatments in oligometastatic patients from prostate cancer
Authors: Franzese Ciro , Zucali Paolo Andrea , Di Brina Lucia , D'Agostino Giuseppe , Navarria Pierina , Franceschini Davide , Santoro Armando , Scorsetti Marta
Published: August 2018

Background

Diagnoses of oligometastatic prostate cancer (PC) increased in the recent years thanks to the advancement in imaging and more effective systemic therapies. Here we evaluate the efficacy of Stereotactic Body Radiation Therapy (SBRT) in oligorecurrent and oligoprogressive PC.

Methods

We included patients with a maximum of five metastases diagnosed in a maximum of two target organs. Concomitant treatment with hormonal therapies or chemotherapies was allowed. End points of the present study were the outcome in terms of Local control of treated metastases (LC), out‐field progression free survival, overall progression free survival (PFS), and overall survival.

Results

We included in the analysis 64 patients treated on 90 metastases. Fifty (78.1%) patients were treated on lymph nodes, 2 (3.1%) patients simultaneously on lymph node and bone while 10 (15.7%) patients on bone only. Lung metastases were treated in 2 (3.1%) patients. Thirty‐seven (57.81%) were without androgen deprivation therapy when treated with SBRT. Median follow‐up was 15.2 months. Rates of LC at 6‐, 12‐, and 18‐ months were 94%, 88%, and 84%, respectively. Oligoprogressive patients compared to oligorecurrent (HR 9.10, P = 0.049) and prolongation of time from diagnosis of metastases to SBRT (HR 1.03, P = 0.047) were associated with worse LC. Median PFS was 6.6 months (range 1.1‐42.4). Castration resistant patients experienced worse PFS compared to castration sensitive group (HR 2.12, P = 0.021).

Conclusions

Stereotactic body radiation therapy seems to be an effective treatment for metastases from PC. Prospective trials are necessary to better define selection of patients and to evaluate combination of SBRT and new systemic drugs in castration resistant patients.
Rationally Engineered Tandem Facial Amphiphiles for Improved Membrane Protein Stabilization Efficacy
Authors: Das Manabendra , Du Yang , Mortensen Jonas S. , Hariharan Parameswaran , Lee Hyun Sung , Byrne Bernadette , Loland Claus J. , Guan Lan , Kobilka Brian K. , Chae Pil Seok
Published: August 2018

A new family of tandem facial glucosides/maltosides (TFGs/TFMs) for membrane protein manipulation was prepared. The best detergent varied depending on the hydrophobic thickness of the target protein, but ether‐based TFMs (TFM‐C0E, TFM‐C3E, and TFM‐C5E) were notable for their ability to confer higher membrane protein stability than the previously developed amide‐based TFA‐1 (P. S. Chae, K. Gotfryd, J. Pacyna, L. J. W. Miercke, S. G. F. Rasmussen, R. A. Robbins, R. R. Rana, C. J. Loland, B. Kobilka, R. Stroud, B. Byrne, U. Gether, S. H. Gellman, J. Am. Chem. Soc. 2010, 132, 16750–16752). Thus, this study not only introduces novel agents with the potential to be used in membrane protein research but also highlights the importance of both the hydrophobic length and linker functionality of the detergent in stabilizing membrane proteins.