bluuebunny/crossref_metadata_2025 huggingface dataset:
Expanded Analogs of Three‐Dimensional Lead‐Halide Hybrid Perovskites
Authors: Umeyama Daiki , Leppert Linn , Connor Bridget A. , Manumpil Mary Anne , Neaton Jeffrey B. , Karunadasa Hemamala I.
Published: July 2020

Replacing the Pb−X octahedral building unit of AIPbX3 perovskites (X=halide) with a pair of edge‐sharing Pb−X octahedra affords the expanded perovskite analogs: AIIPb2X6. We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium‐based cations with low‐lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium‐based orbitals in the band gap transition of AIIPb2X6. The organic‐molecule‐based conduction band and the inorganic‐ion‐based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.
Revealing the A‐Site Effect of Lead‐Free A3Sb2Br9 Perovskite in Photocatalytic C(sp3)−H Bond Activation
Authors: Zhang Zhenzhen , Yang Yuying , Wang Yingying , Yang Lanlan , Li Qi , Chen Langxing , Xu Dongsheng
Published: July 2020

The lead‐free halide perovskite A3Sb2Br9 is utilized as a photocatalyst for the first time for C(sp3)−H bond activation. A3Sb2Br9 nanoparticles (A3Sb2Br9 NPs) with different ratios of Cs and CH3NH3 (MA) show different photocatalytic activities for toluene oxidation and the photocatalytic performance is enhanced when increasing the amount of Cs. The octahedron distortion caused by A‐site cations can change the electronic properties of X‐site ions and further affect the electron transfer from toluene molecules to Br sites. After the regulation of A‐site cations, the photocatalytic activity is higher with A3Sb2Br9 NPs than that with classic photocatalysts (TiO2, WO3, and CdS). The main active species involved in photocatalytic oxidation of toluene are photogenerated holes (h+) and superoxide anions (.O2−). The octahedron distortion by A‐site cations affecting photocatalytic activity remains unique and is also a step forward for understanding more about halide‐perovskite‐based photocatalysis. The relationship between octahedron distortion and photocatalysis can also guide the design of new photocatalytic systems involving other halide perovskites.
Kombination von DNA‐Origami und Polymeren: Eine leistungsstarke Methode zum Aufbau definierter Nanostrukturen
Authors: Hannewald Nadine , Winterwerber Pia , Zechel Stefan , Ng David Y. W. , Hager Martin D. , Weil Tanja , Schubert Ulrich S.
Published: July 2020

Die Kombination von DNA‐Origami‐Nanostrukturen und Polymeren bietet neue Möglichkeiten für die Herstellung definierter Strukturen im 100‐nm‐Bereich. Im Allgemeinen dient hierbei das DNA‐Origami als vielseitige Vorlage für die hochspezifische Anordnung von Polymerketten. Polymer‐DNA‐Hybrid‐Nanostrukturen können durch Synthese des Polymers direkt auf der DNA‐Matrix oder durch Anknüpfung vorgeformter Polymere an das DNA‐Gerüst hergestellt werden. Diese Konjugationen können kovalenter Natur sein oder auf einer Basenpaarhybridisierung zwischen entsprechend modifizierten Polymeren und DNA‐Origami beruhen. Darüber hinaus ermöglicht das negativ geladene DNA‐Gerüst die Wechselwirkung mit positiv geladenen Polyelektrolyten unter Bildung stabiler Komplexe. Die Kombination von Polymeren mit einstellbaren Eigenschaften und DNA‐Origami ermöglicht die Herstellung einer neuen Klasse von Hybridmaterialien mit möglichen Anwendungen für den Energietransfer, Schaltkreise im Nanomaßstab oder die Templat‐gesteuerte Synthese von Polymerstrukturen mit Nanomustern.
Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2
Authors: Oró‐Solé Judith , Fina Ignasi , Frontera Carlos , Gàzquez Jaume , Ritter Clemens , Cunquero Marina , Loza‐Alvarez Pablo , Conejeros Sergio , Alemany Pere , Canadell Enric , Fontcuberta Josep , Fuertes Amparo
Published: July 2020

Non‐centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2, which shows a polar 6H polytype. Synchrotron X‐ray and neutron powder diffraction, and annular bright‐field in scanning transmission electron microscopy indicate that it crystalizes in the non‐centrosymmetric space group P63mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second‐order Jahn–Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face‐sharing octahedra that lead to long‐range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.
Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process
Authors: Qiao Chang , Villar‐Yanez Alba , Sprachmann Josefine , Limburg Bart , Bo Carles , Kleij Arjan W.
Published: July 2020

A conceptually novel approach is described for the synthesis of six‐membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five‐membered cyclic carbonates having a β‐positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N‐heterocyclic base allows equilibration towards a thermodynamically disfavored six‐membered carbonate analogue that can be trapped by an acylating agent. Various control experiments and computational analysis of this manifold are in line with a process that is primarily dictated by a kinetically controlled acylation step. This cascade process delivers an ample diversity of six‐membered cyclic carbonates in excellent yields and chemoselectivities under mild reaction conditions.
Functional Genome Mining Reveals a Class V Lanthipeptide Containing a d‐Amino Acid Introduced by an F420H2‐Dependent Reductase
Authors: Xu Min , Zhang Fei , Cheng Zhuo , Bashiri Ghader , Wang Jing , Hong Jiali , Wang Yemin , Xu Lijun , Chen Xuefei , Huang Sheng‐Xiong , Lin Shuangjun , Deng Zixin , Tao Meifeng
Published: July 2020

Lantibiotics are a type of ribosomally synthesized and post‐translationally modified peptides (termed lanthipeptides) with often potent antimicrobial activity. Herein, we report the discovery of a new lantibiotic, lexapeptide, using the library expression analysis system (LEXAS) approach. Lexapeptide has rare structural modifications, including N‐terminal (N,N)‐dimethyl phenylalanine, C‐terminal (2‐aminovinyl)‐3‐methyl‐cysteine, and d‐Ala. The characteristic lanthionine moiety in lexapeptide is formed by three proteins (LxmK, LxmX, and LxmY), which are distinct from enzymes known to be involved in lanthipeptide biosynthesis. Furthermore, a novel F420H2‐dependent reductase (LxmJ) from the lexapeptide biosynthetic gene cluster (BGC) is identified to catalyze the reduction of dehydroalanine to install d‐Ala. Our findings suggest that lexapeptide is the founding member of a new class of lanthipeptides that we designate as class V. We also identified further class V lanthipeptide BGCs in actinomycetes and cyanobacteria genomes, implying that other class V lantibiotics await discovery.
Atom Exchange Versus Reconstruction: (GexAs4−x)x− (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au6(Ge3As)(Ge2As2)3]3−
Authors: Pan Fuxing , Guggolz Lukas , Weigend Florian , Dehnen Stefanie
Published: July 2020

The Zintl anion (Ge2As2)2− represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh3)AuMe] into the 1,2‐diaminoethane (en) solution of (Ge2As2)2−, the heterometallic cluster anion [Au6(Ge3As)(Ge2As2)3]3− is obtained as its salt [K(crypt‐222)]3[Au6(Ge3As)(Ge2As2)3]⋅en⋅2 tol (1). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (GexAs4−x)x− (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge3As)3− unit besides three (Ge2As2)2− units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au6(Ge3As)(Ge2As2)3]3−. Reactions of the heavier homologues (Tt2Pn2)2− (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1, but dimers of ternary nine‐vertex clusters, {[AuTt5Pn3]2}4− (in 2–4; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge2As2)2−, according to the DFT calculations.
S6N2O15—A Nitrogen‐Poor Sulfur Nitride Oxide, and the Anhydride of Nitrido‐tris‐Sulfuric Acid
Authors: van Gerven David , Wickleder Mathias S.
Published: July 2020

The reaction of hexachlorophosphazene, P3N3Cl6, with SO3 leads to the new sulfur nitride oxide S6N2O15. The compound displays an extraordinarily low nitrogen content and exhibits a bicyclic cage structure according to the formulation N{S(O)2O(O)2S}3N, with both nitrogen atoms in trigonal planar coordination of sulfur atoms. Interestingly, the new nitride oxide can be also seen as the anhydride of nitrido‐tris‐sulfuric acid, N(SO3H)3.
Diversified Excited‐State Relaxation Pathways of Donor–Linker–Acceptor Dyads Controlled by a Bent‐to‐Planar Motion of the Donor
Authors: Sun Guangchen , Wei Yu‐Chen , Zhang Zhiyun , Lin Jia‐An , Liu Zong‐Ying , Chen Wei , Su Jianhua , Chou Pi‐Tai , Tian He
Published: July 2020

Herein, we introduce the cyclic 8π‐electron (C8π) molecule N,N′‐diaryl‐dihydrodibenzo[a,c]phenazine (DPAC) as a dual‐functional donor to establish a series of new donor–linker–acceptor (D–L–A) dyads DLA1–DLA5. The excited‐state bent‐to‐planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1–A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited‐state electron transfer vs. energy transfer can be finely harnessed, which is verified via steady‐state spectroscopy and time‐resolved emission measurements. This comprehensive approach demonstrates, for the first time, the manifold of excited‐state properties governed by bifunctional donor‐based D–L–A dyads, including bent‐to‐planar, photoinduced electron transfer (PET) from excited donor to acceptor (oxidative‐PET), fluorescence resonance energy transfer (FRET), bent‐to‐planar followed by electron transfer (PFET), and PET from donor to excited acceptor (reductive‐PET).
Titanium Defective Sites in TS‐1: Structural Insights by Combining Spectroscopy and Simulation
Authors: Signorile Matteo , Braglia Luca , Crocellà Valentina , Torelli Piero , Groppo Elena , Ricchiardi Gabriele , Bordiga Silvia , Bonino Francesca
Published: July 2020

Ti silicates, and in particular, titanium silicalite‐1 (TS‐1), are nowadays important catalysts for several partial oxidation reactions in the presence of aqueous H2O2 as an oxidant. Despite the numerous studies dealing with this material, some fundamental aspects are still unclear. In particular, the structure and the catalytic role of defective Ti sites, other than perfect tetrahedral sites recognized as the main active species, has not been quantitatively discussed in the literature. We assess the structural features of defective Ti sites on the basis of outcomes of electronic spectroscopies, as interpreted through quantum mechanical simulation. Strong evidence is disclosed to support the fact that the most common defective Ti sites, often reported in the TS‐1 literature, are monomeric Ti centers that are embedded in the zeolite framework, and which have a distorted octahedral local symmetry.
Peptide‐Conjugated Long‐Lived Theranostic Imaging for Targeting GRPr in Cancer and Immune Cells
Authors: Wang Wanhe , Wu Ke‐Jia , Vellaisamy Kasipandi , Leung Chung‐Hang , Ma Dik‐Lung
Published: July 2020

Gastrin‐releasing peptide receptor (GRPr) plays proliferative and inflammatory roles in living systems. Here, we report a highly selective GRPr antagonist (JMV594)‐tethered iridium(III) complex for probing GRPr in living cancer cells and immune cells. This probe exhibited desirable photophysical properties and also displayed negligible cytotoxicity, overcoming the inherent toxicity of the iridium(III) complex. Its long emission lifetime enabled its luminescence signal to be readily distinguished from the interfering fluorescence of organic dyes by using a time‐resolved technique. This probe selectively visualized living cancer cells via specific binding to GRPr, while it also modulated the function of GRPr on TNF‐α secretion in immune cells. To our knowledge, this is the first peptide‐conjugated iridium(III) complex developed as a GRPr bioimaging probe and modulator of GRPr activity. This theranostic agent shows great potential at unmasking the diverse roles of GRPr in living systems.
A Separation‐Sensing Membrane Performing Precise Real‐Time Serum Analysis During Blood Drawing
Authors: Chu Zhenyu , Zhang Wei , You Qiannan , Yao Xiaoyue , Liu Tao , Liu Gongping , Zhang Guangru , Gu Xiaoping , Ma Zhengliang , Jin Wanqin
Published: July 2020

Dynamic and on‐site analysis of serum from human blood is crucial, however, state‐of‐the‐art blood‐assay methods can only collect single or discrete data of physiological analytes; thus, the online reports of the dynamic fluctuation of key analytes remains a great challenge. Here, we propose a novel separation‐sensing membrane by constructing a heterogeneous‐nanostructured architecture, wherein a surface nanoporous layer continuously extracts serum, while the biosensing nanochannels underneath dynamically recognise biotargets, thereby achieving a continuous testing of vital clinical indices as blood is drawn. By precisely controlling the pore structure and nanoshape of biosensing crystals, this membrane achieved accurate and online glucose and lactate monitoring in patients with a variety of medical conditions within 1 min, which is one order of magnitude faster than state‐of‐the‐art techniques. Moreover, various kinds of bio‐recognisers can be introduced into this membrane to accurately detect glutamate, transaminase, and cancer biomarkers.
Nonlinear predictive control employing Carleman bilinearization and fixed search directions
Authors: Resende Pereira Henrique William , Kawakami Harrop Galvão Roberto , Yoneyama Takashi
Published: July 2020

This work is concerned with the predictive control of nonlinear systems using the Carleman bilinearization technique. Given a nonlinear system model with sufficient regularity, a bilinear approximation can be obtained by means of Carleman's technique. After discretizing the continuous time model, several algorithms exist to tackle the bilinear model predictive control (BMPC) problem. More specifically, the present work exploits the combination of Carleman's approximation with a fixed search directions algorithm previously proposed within the context of BMPC. Simulations are carried out in order to compare predictive controllers designed using bilinear and linear plant models, but acting on the original nonlinear system. Moreover, the fixed search directions algorithm is compared with the use of a standard interior point optimizer. As a result, the proposed method is shown to provide improvements in terms of either stability, constraint satisfaction or reduced computational effort.
Improving lysine production through construction of an Escherichia coli enzyme‐constrained model
Authors: Ye Chao , Luo Qiuling , Guo Liang , Gao Cong , Xu Nan , Zhang Li , Liu Liming , Chen Xiulai
Published: July 2020

Microbial cell factories are widely used for the production of high‐value chemicals. However, maximizing production titers is made difficult by the complicated regulatory mechanisms of these cell platforms. Here, kcat values were incorporated to construct an Escherichia coli enzyme‐constrained model. The resulting ec_iML1515 model showed that the protein demand and protein synthesis rate were the key factors affecting lysine production. By optimizing the expression of the 20 top‐demanded proteins, lysine titers reached 95.7 ± 0.7 g/L, with a 0.45 g/g glucose yield. Moreover, adjusting NH4+ and dissolved oxygen levels to regulate the synthesis rate of energy metabolism‐related proteins caused lysine titers and glucose yields to increase to 193.6 ± 1.8 g/L and 0.74 g/g, respectively. The ec_iML1515 model provides insight into how enzymes required for the biosynthesis of certain products are distributed between and within metabolic pathways. This information can be used to accurately predict and rationally design lysine production.
Formulation and production of a blood‐free and chemically defined virus production media for VERO cells
Authors: Alfano Randall , Pennybaker Atherly , Halfmann Peter , Huang Claire Y.‐H.
Published: July 2020

Vaccines provide effective protection against many infectious diseases as well as therapeutics for select pathologies, such as cancer. Many viral vaccines require amplification of virus in cell cultures during manufacture. Traditionally, cell cultures, such as VERO, have been used for virus production in bovine serum‐containing culture media. However, due to concerns of potential adventitious agents present in fetal bovine serum (FBS), regulatory agencies suggest avoiding the use of bovine serum in vaccine production. Current serum‐free media suitable for VERO‐based virus production contains high concentrations of undefined plant hydrolysates. Although these media have been extensively used, the lack of chemical definition has the potential to adversely affect cell growth kinetics and subsequent virus production. As plant hydrolysates are made from plant raw materials, performance variations could be significant among different lots of production. We developed a chemically defined, serum‐free medium, OptiVERO, which was optimized specifically for VERO cells. VERO cell growth kinetics were demonstrated to be equivalent to EMEM‐10% FBS in this chemically defined medium while the plant hydrolysate‐containing medium demonstrated a slower doubling time in both two‐dimensional (2D) and 3D cultures. Virus production comparisons demonstrated that the chemically defined OptiVERO medium performed at least as good as the EMEM‐10%FBS and better than the plant hydrolysate‐containing media. We report the success in using recombinant proteins to replace undefined plant hydrolysates to formulate a chemically defined medium that can efficiently support VERO cell expansion and virus production.
Macrocyclization of a Ligand Targeting a Toxic RNA Dramatically Improves Potency
Authors: Benhamou Raphael I. , Vezina‐Dawod Simon , Choudhary Shruti , Won Wang Kye , Meyer Samantha M. , Yildirim Ilyas , Disney Matthew D.
Published: July 2020

RNA molecules both contribute to and are causative of many human diseases. One method to perturb RNA function is to target its structure with small molecules. However, discovering bioactive ligands for RNA targets is challenging. Here, we show that the bioactivity of a linear dimeric ligand that inactivates the RNA trinucleotide repeat expansion that causes myotonic dystrophy type 1 [DM1; r(CUG)exp] can be improved by macrocyclization. Indeed, the macrocyclic compound is ten times more potent than the linear compound for improving DM1‐associated defects in cells, including in patient‐derived myotubes (muscle cells). This enhancement in potency is due to the macrocycle's increased affinity and selectively for the target, which inhibit r(CUG)exp’s toxic interaction with muscleblind‐like 1 (MBNL1), and its superior cell permeability. Macrocyclization could prove to be an effective way to enhance the bioactivity of modularly assembled ligands targeting RNA.
Controlled Self‐Assembly of Metallacycle‐Bridged Gold Nanoparticles for Surface‐Enhanced Raman Scattering
Authors: Zheng Wei , Yang Xiao‐Lei , Wu Gui‐Yuan , Cheng Lin
Published: July 2020

In this work, well‐defined two‐dimensional metallacycles have been successfully employed for the well‐controlled self‐assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well‐defined system for studying the hot‐spot phenomenon in surface‐enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing.
Single‐Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2–3/2 Spin Admixture
Authors: Viciano‐Chumillas Marta , Blondin Geneviève , Clémancey Martin , Krzystek Jurek , Ozerov Mykhaylo , Armentano Donatella , Schnegg Alexander , Lohmiller Thomas , Telser Joshua , Lloret Francesc , Cano Joan
Published: July 2020

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single‐ion magnet behaviour, is reported. This behaviour originates from the close proximity (≈550 cm−1) of the intermediate‐spin S=3/2 excited states to the high‐spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin‐admixture model evidences a sizable contribution (≈15 %) of S=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm−1). Frequency‐domain EPR spectroscopy allowed the mS= |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero‐field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field‐domain EPR studies are consistent with this model, which is also supported by theoretical calculations.
Surface Modification Strategies for Improving the Cycling Performance of Ni‐Rich Cathode Materials
Authors: Weber Daniel , Tripković Đorđije , Kretschmer Katja , Bianchini Matteo , Brezesinski Torsten
Published: July 2020

Ni‐rich layered lithium metal oxides are the cathode active materials of choice for high‐energy‐density Li‐ion batteries. While the high content of Ni is responsible for the excellent capacity, it is also the source of interfacial instability, limiting the material's lifetime due to a variety of correlated in‐ and extrinsic factors. Hence, reconciling the opposing trends of high Ni content and long‐term cycling stability by modifying the material's surface is one of the challenges in the field. Here, we review various studies on surface modification of Ni‐rich (≥ 80 %) layered cathode active materials in order to categorize current research efforts. Broadly, the three strategies of coating, surface doping and washing are discussed, each with their advantages and shortcomings. In conclusion, we highlight new directions of research that could bring Ni‐rich layered lithium metal oxide cathodes from the laboratory to the real world.
Promoting Culturally Responsive and Equitable Evaluation With Latinx Immigrants
Authors: Lemos Diana , Garcia David
Published: July 2020

Culturally Responsive and Equitable Evaluation requires evaluators to understand the social and intersectional identity experienced by Hispanic/Latino/Latinx communities, inclusive of immigrants in the United States. This chapter introduces relevant issues for evaluators to consider when working with Latinx immigrants. Evaluators must simultaneously address biases that people have toward Latinx immigrants; heed intergroup diversity among Latino immigrants, and increase Latinx immigrants' knowledge about their existing environment and their ability to advocate for themselves. Likewise, they must advocate for change in policies and practices of public, private, and nonprofit institutions to be more welcoming and responsive to Latinx immigrants' needs; build social support and foster a shared sense of community between immigrants and their communities, and transform the way multiple institutions with related goals and services work together to provide more seamless support to Latinx immigrants. Furthermore, stakeholders must be involved in the change process, with data made available at the stakeholder level to incite change. Therefore, evaluators must spend adequate time during the design phase to align their understanding, expectations, and strategies. Evaluators working collaboratively with diverse Latinx immigrants ensures these perspectives are integrated throughout the process and to address unanticipated challenges.
Blest Be the Tie That Binds
Authors: Hall Melvin E.
Published: July 2020

This chapter explores the relationship between program evaluation and social change through the lens of key historical periods in the development of the field. Also profiled is the relationship between the practice of program evaluation by evaluators, and the communities or contexts in which the evaluand is situated. And finally, the chapter explores the strong bonds that support group consciousness and a desire for change. “Oppositional Consciousness,” a sociological construct, serves as a heuristic that may be useful for program evaluators seeking to promote, support, or inspire social change.
Mid‐Holocene environmental change and human occupation at Sai Island, Northern Sudan
Authors: Adelsberger Katherine A. , Lewis Jonathan , Dodd Justin P. , Hill Danika , Smith Jennifer R. , Garcea Elena A. A.
Published: July 2020

Holocene environmental change in the northern and central Nile Valley was controlled primarily by shifts in the Intertropical Convergence Zone over time, leading to changes in aridity and water availability for early occupants of the region. Although local environmental changes may help to motivate societal changes such as those in settlement patterns or technological productions, evidence from pedogenic carbonates at Sai Island, in northern Sudan, indicate that the most significant environmental changes predated a key shift in local food production from foraging to pastoralism. Changes in local environmental conditions from a wetter and more diverse vegetative context to a more arid and C4‐dominant landscape occurred during the occupation of Khartoum Variant foragers, whereas later Abkan pastoralists arrived without any notable differences in the region compared to the environments inhabited by the most recent foragers. The lack of an external environmental driver for food production changes at Sai suggests that other, potentially cultural factors were more important in these economic decisions in the mid‐Holocene.
Longitudinal validity of PET‐based staging of regional amyloid deposition
Authors: Jelistratova Irina , Teipel Stefan J. , Grothe Michel J.
Published: July 2020

Positron emission tomography (PET)‐based staging of regional amyloid deposition has recently emerged as a promising tool for sensitive detection and stratification of pathology progression in Alzheimer's Disease (AD). Here we present an updated methodological framework for PET‐based amyloid staging using region–specific amyloid‐positivity thresholds and assess its longitudinal validity using serial PET acquisitions. We defined region‐specific thresholds of amyloid‐positivity based on Florbetapir‐PET data of 13 young healthy individuals (age ≤ 45y), applied these thresholds to Florbetapir‐PET data of 179 cognitively normal older individuals to estimate a regional amyloid staging model, and tested this model in a larger sample of patients with mild cognitive impairment (N = 403) and AD dementia (N = 85). 2‐year follow‐up Florbetapir‐PET scans from a subset of this sample (N = 436) were used to assess the longitudinal validity of the cross‐sectional model based on individual stage transitions and data‐driven longitudinal trajectory modeling. Results show a remarkable congruence between cross‐sectionally estimated and longitudinally modeled trajectories of amyloid accumulation, beginning in anterior temporal areas, followed by frontal and medial parietal areas, the remaining associative neocortex, and finally primary sensory‐motor areas and subcortical regions. Over 98% of individual amyloid deposition profiles and longitudinal stage transitions adhered to this staging scheme of regional pathology progression, which was further supported by corresponding changes in cerebrospinal fluid biomarkers. In conclusion, we provide a methodological refinement and longitudinal validation of PET‐based staging of regional amyloid accumulation, which may help improving early detection and in‐vivo stratification of pathologic disease progression in AD.
Synthesis, characterization, density functional theory, thermal, antimicrobial efficacy, and DNA binding/cleavage studies of Cu(II), Cr(III), Fe(III), Ni(II), Co(II), Zn(II), and Pt(IV) complexes with a derivative of 2‐hydroxyphenoxymethylfuran‐5‐carbaldehyde
Authors: Al‐Mohaimeed Amal M. , Al‐Farraj Eida S. , Al‐Onazi Wedad A. , Alothman Asma A. , Almarhoon Zainab M.
Published: July 2020

In this study, Seven new complexes incorporating (E)‐2‐(((5‐([2‐hydroxyphenoxy]methyl)furan‐2‐yl)methylene)amino)phenol derived from 2‐hydroxyphenoxymethylfuran‐5‐carbaldehyde and 2‐aminophenol have been synthesized using Cu(II), Cr(III), Fe(III), Ni(II), Co(II), Zn(II), and Pt(IV) metal salts. Thermal measurements, molar conductance, magnetic moment, elemental analyses, spectral (IR, UV–Vis, 1H nuclear magnetic resonance (NMR), ESR, Mass), were used to characterize insulated solid complexes. The thermogravimetry (TG) and differential thermoanalysis (DTA) of the complexes were carried out in the range of 30–900°C. Magnetic susceptibility and electronic spectral data, as well as quantum chemical calculations, reveal the square planar geometry for Ni (II) complex, square planar/octahedral geometry for Cu (II) complex, while Co(II), Zn(II), Cr(III), Fe(III), and Pt (IV) complexes are octahedral geometry. Density functional theory (DFT) studies revealed that geometries of metal complexes and Schiff base were entirely optimized in relation to use energy by 6–31 + g (d,p) basis set. The complexes show a well‐defined crystal system indicated by a powder‐X‐ray diffraction pattern. The scanning electron microscope showed complexes were nanocrystalline in nature, in addition to the interaction of the complexes with calf thymus CT‐DNA, which was investigated via the UV–visible absorption method. Therefore, the DNA cleavage activity by the H2L ligand and its metal complexes was performed. Finally, the synthesized complexes were tested for their in‐vitro antimicrobial efficacy.
Characterization of the Arion vulgaris pedal gland system
Authors: Greistorfer Sophie , Suppan Johannes , Cyran Norbert , Klepal Waltraud , Farkas Robert , Rudoll Livia , von Byern Janek
Published: July 2020

The most common European gastropod species, Arion vulgaris, is one of the most troublesome pests for private garden owners and commercial agriculturists. The sticky and hard to remove secretion produced by these animals allows them to overcome most artificial and natural barriers. However, this highly adherent biopolymer has recently shown great potential for novel wound‐healing applications in medicine. Nevertheless, our knowledge of the underlying gland system is still limited and few studies on the ventral gland system are available. We studied the lateral and ventral pedal glands in Arion vulgaris to determine their secretory content histochemically and through lectin assays. Using these histological and histochemical methods we differentiate five gland types with different mucus composition in the lateral pedal region of the foot of Arion vulgaris. These contain sulphated and carboxylated mucosubstances (positive Alcian blue staining) but lack hexose‐containing mucosubstances (negative PAS staining). In the ventral pedal region, four gland types can be differentiated producing sulphated and carboxylated mucosubstances. Within the ventral mucus, a high affinity for the lectins PNA and WGA is observed. While the lateral glands are histochemically negative for PAS, a positive staining with the lectin JAC is observed. Arion vulgaris shows clear morphological differences from other arionid species. This raises the question whether the variation in the chemistry of the secretory material and mucus composition is the result of different functions and/or is related to the animals' different environmental conditions. A comparison of some glands of Arion vulgaris with those of the helicid species Helix pomatia and Cepaea hortensis indicates morphological similarities.
The potential impacts of early secreted antigenic target of 6 kDa of Mycobacterium tuberculosis on KSHV‐infected cells
Authors: Dai Lu , Jung Bock‐Gie , Chen Jungang , Samten Buka , Forrest James Craig , Post Steven R. , Qin Zhiqiang
Published: July 2020

Kaposi's sarcoma‐associated herpesvirus (KSHV) causes several human cancers, including Kaposi's sarcoma (KS) and primary effusion lymphoma, which are mostly seen in immunocompromised patients, such as human immunodefeciency virus (HIV)+ individuals. Tuberculosis (TB), caused by the bacterial pathogen Mycobacterium tuberculosis (Mtb), remains one of the deadliest infectious diseases in the world. The risk of developing TB is dramatically higher in people living with HIV than among those without HIV infection. Case reports link cutaneous or pulmonary KS in HIV+ patients with mycobacterial co‐infections, however, impacts of Mtb infection or its products on KSHV‐infected cells are not known. We report here that ESAT‐6, a secreted Mtb virulence factor, induces viral reactivation from KSHV‐infected cells. KSHV‐infected pulmonary endothelial cells were resistant to ESAT‐6 induced inhibition of cell growth. Our data demonstrate that Mtb virulence factors influence the biology of KSHV‐infected cells, highlighting the need to study the interactions between these two pathogens commonly found in people living with HIV.
Development of a monoclonal antibody‐based antigen capture enzyme‐linked immunosorbent assay for detection of H7N9 subtype avian influenza virus
Authors: Yang Fan , Xiao Yixin , Liu Fumin , Yao Hangping , Wu Nanping , Wu Haibo
Published: July 2020

To establish a rapid detection method for H7N9 avian influenza virus (AIV), monoclonal antibodies (mAbs) against hemagglutinin (HA) of H7N9 were developed to establish an antigen‐capture enzyme‐linked immunosorbent assay (AC‐ELISA). AC‐ELISA achieved high specificity and sensitivity, with a detection limit of 3.9 ng/mL for H7N9 HA protein (A/Zhejiang/DTID‐ZJU01/2013), and 2−2 HA unit/100 μL for live H7N9 AIV. The inter‐ and intra‐assay coefficient of variation was less than 10%. Compared with conventional virus isolation detection, the sensitivity and specificity were 94.96% and 88.24%, respectively. AC‐ELISA proved to be a rapid and practical technique for the detection of H7N9 AIV.
Factors associated with unsuccessful pessary fitting in women with symptomatic pelvic organ prolapse: Systematic review and metanalysis
Authors: de Albuquerque Coelho Suelene Costa , Brito Luiz Gustavo Oliveira , de Araujo Camila Carvalho , Juliato Cássia Raquel Teatin
Published: July 2020

Aims

To identify the factors associated with unsuccessful pessary fitting and reasons for discontinuation for women with symptomatic pelvic organ prolapse (POP).

Methods

This systematic review is registered at the PROSPERO database. We have included all studies, regardless of the study design whose primary outcomes were factors associated with unsuccessful pessary fitting and discontinuation for symptomatic POP women. Exclusion criteria were case series, literature reviews, other forms of conservative treatment. Data selection/extraction was performed by two investigators. For pessary fitting, a meta‐analysis was performed for at least two studies pooled in a forest plot. The risk of bias was classified by the ROBINS‐I and ROB‐2 classification.

Results

From 409 studies retrieved after data search, only twenty‐one articles remained for final analysis (18 cohort studies, 1 cross‐sectional study, and 2 RCTs). Meta‐analysis was performed in nine studies for pessary fitting and the associated factors were: higher body mass index (BMI) (MD = 0.688 [0.233‐1.143]; P = .03; i2 = 0%), previous reconstructive surgery (OR = 1.705 [1.016‐2.860]; P = .043; i2 = 69%) and advanced POP (OR = 4.2 [2.9‐6.1]; P < .05; i2 = 92%). Older age, larger total vaginal length (TVL), and genital hiatus and previous hysterectomy were not associated factors. Regarding discontinuation, thirteen reasons were quoted, and the most frequent were: the desire for surgical treatment (111/3.601), pessary extrusion (385/3.601), and pain/discomfort (163/3.601).

Conclusion

Obese, previously reconstructive pelvic surgery, advanced prolapse are at risk for unsuccessful pessary fitting. Pain is the most quoted reason for discontinuation. These pooled data may help clinicians to identify patients that may not succeed in their attempt for pessary treatment.
In person, online, and up close: the cross‐contextual consistency of expressive accuracy
Authors: Human Lauren J. , Rogers Katherine H. , Biesanz Jeremy C.
Published: July 2020

People vary widely in their expressive accuracy, the tendency to be viewed in line with one’s unique traits. It is unclear, however, whether expressive accuracy is a stable individual difference that transcends social contexts or a more piecemeal, context‐specific characteristic. The current research therefore examined the consistency of expressive accuracy across three social contexts: face‐to‐face initial interactions, close relationships, and social media. There was clear evidence for cross‐contextual consistency, such that expressive accuracy in face‐to‐face first impressions, based on brief round‐robin interactions, was associated with expressive accuracy with close others (Sample 1; Ntargets = 514; Ndyads = 1656) and based on Facebook profiles (Samples 2 and 3: Ntargets = 126–132; Ndyads = 1170–1476). This was found on average across traits and for high and low observability traits. Further, unique predictors emerged for different types of expressive accuracy, with psychological adjustment and conscientiousness most consistently linked to overall expressive accuracy, extraversion most consistently linked to high observability expressive accuracy, and neuroticism most consistently linked to low observability expressive accuracy. In sum, expressive accuracy appears to emerge robustly and consistently across contexts, although its predictors may differ depending on the type of trait.
Integration of mental health screening and treatment into cystic fibrosis clinics: Evaluation of initial implementation in 84 programs across the United States
Authors: Quittner Alexandra L. , Abbott Janice , Hussain Saida , Ong Thida , Uluer Ahmet , Hempstead Sarah , Lomas Paula , Smith Beth
Published: July 2020

Background

A large‐scale epidemiological study of 6088 individuals with cystic fibrosis (CF) and 4102 caregivers in nine countries documented elevated symptoms of depression and anxiety, leading to international guidelines for annual screening and follow‐up. To facilitate national implementation, 84 CF programs funded a mental health coordinators (MHC). Implementation was evaluated after 1 year using the consolidated framework for implementation research (CFIR) to identify facilitators and barriers.

Methods

A 45‐item internet survey was developed to assess relevant CFIR implementation steps. Surveys were completed in 2016. It assessed five domains tailored to study aims: (a) Intervention characteristics, (b) outer setting, (c) inner setting, (d) characteristics of individuals, and (e) process of implementation.

Results

Response rate was 88%, with pediatric and adult programs equally represented. A majority of MHCs were social workers (54.1%) and psychologists (41.9%); 41% had joined the team in the past year. Facilitators across the five domains included universal uptake of screening tools, greater awareness and detection of psychological symptoms, reduced stigma, and positive feedback from patients and families. Barriers included limited staff time, space, and logistics.

Discussion

This is the largest systematic effort to integrate mental health screening and treatment into the care of individuals with a serious, chronic illness and their caregivers. MHCs implementing screening, interpretation and follow‐up reported positive results, and significant barriers. This national implementation effort demonstrated that depression and anxiety can be efficiently evaluated and treated in a complex, chronic disease. Future efforts include recommending the addition of screening scores to national CF Registries and examining their effects on health outcomes.
Neuroendocrine differentiation in usual‐type prostatic adenocarcinoma: Molecular characterization and clinical significance
Authors: Kaur Harsimar , Samarska Iryna , Lu Jiayun , Faisal Farzana , Maughan Benjamin L. , Murali Sanjana , Asrani Kaushal , Alshalalfa Mohamed , Antonarakis Emmanuel S. , Epstein Jonathan I. , Joshu Corinne E. , Schaeffer Edward M. , Mosquera Juan Miguel , Lotan Tamara L.
Published: July 2020

Background

Small cell neuroendocrine (NE) carcinomas of the prostate classically lose androgen receptor (AR) expression, may harbor loss of the RB1, TP53, and PTEN tumor suppressor genes, and are associated with a poor prognosis. However usual‐type adenocarcinomas may also contain areas of NE differentiation, and in this context the molecular features and biological significance are less certain.

Methods

We examined the molecular phenotype and oncologic outcomes of primary prostate adenocarcinomas with ≥5% NE differentiation (≥5% chromogranin A‐positive NE cells in any given tumor spot on tissue microarray) using three independent study sets: a set of tumors with paneth cell‐like NE differentiation (n = 26), a retrospective case‐cohort of intermediate‐ and high‐risk patients enriched for adverse outcomes (n = 267), and primary tumors from a retrospective series of men with eventual castration‐resistant metastatic prostate cancer (CRPC) treated with abiraterone or enzalutamide (n = 55).

Results

Benign NE cells expressed significantly lower quantified AR levels compared with paired benign luminal cells (P < .001). Similarly, paneth‐like NE carcinoma cells or carcinoma cells expressing chromogranin A expressed significantly lower quantified AR levels than paired non‐NE carcinoma cells (P < .001). Quantified ERG protein expression, was also lower in chromogranin A‐labeled adenocarcinoma cells compared with unlabeled cells (P < .001) and tumors with NE differentiation showed lower gene expression scores for AR activity compared with those without. Despite evidence of lower AR signaling, adenocarcinomas with NE differentiation did not differ by prevalence of TP53 missense mutations, or PTEN or RB1 loss, compared with those without NE differentiation. Finally, NE differentiation was not associated with time to metastasis in intermediate‐ and high‐risk patients (P = .6 on multivariate analysis), nor with progression‐free survival in patients with CRPC treated with abiraterone or enzalutamide (P = .9).

Conclusion

NE differentiation in usual‐type primary prostate adenocarcinoma is a molecularly and clinically distinct form of lineage plasticity from that occurring in small cell NE carcinoma.
Baseline susceptibility and resistance allele frequency in Ostrinia furnacalis related to Cry1 toxins in the Huanghuaihai summer corn region of China
Authors: Li Guoping , Huang Jianrong , Ji Tingjie , Tian Caihong , Zhao Xincheng , Feng Hongqiang
Published: July 2020

BACKGROUND

Ostrinia furnacalis (Guenée) is one of the most destructive pests of corn and is a major target of transgenic corn expressing Bt (Bacillus thuringiensis) toxins in the Huanghuaihai summer corn region of China. Prior to the widespread commercialization of transgenic Bt corn, it is necessary to estimate baseline susceptibility to Bt toxins and Bt toxin resistance allele frequencies in O. furnacalis.

RESULTS

The median lethal concentration (LC50) values of the Bt toxins Cry1Ab, Cry1Ac and Cry1F for 15 different populations ranged from 0.887 to 1.617, 1.251 to 2.594 and 4.146 to 6.465 ng cm−2, respectively. The LC99 values of 93, 45, and 197 ng cm−2 for Cry1Ab, Cry1Ac and Cry1F, respectively, killed > 99% of individuals of eight O. furnacalis populations collected in 2017 and were identified as diagnostic concentrations for monitoring susceptibility in O. furnacalis populations in this region. Using the F2 screening method with these diagnostic concentrations, the resistance allele frequencies related to Cry1Ab, Cry1Ac and Cry1F were found to be 0.002 (0.000283–0.006484), 0.001 (0.000030–0.004295) and 0.001 (0.000030–0.004295), respectively, in 2018.

CONCLUSION

Fifteen populations of O. furnacalis collected in the Huanghuaihai summer corn region of China were all susceptible to Cry1Ab, Cry1Ac and Cry1F toxins, and the susceptibility showed no significant variation among these O. furnacalis populations. The estimated resistance allele frequency to Cry1Ab, Cry1Ac and Cry1F was rare in this region. This provided essential knowledge for making the decision to commercialize Bt maize, and monitoring resistance development and evaluating resistance management strategies in the future in the Huanghuaihai summer corn region of China. © 2020 Society of Chemical Industry