bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractThe 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

AbstractThe 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

AbstractHerein, 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

AbstractTi 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

AbstractGastrin‐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

AbstractDynamic 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

AbstractThis 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

AbstractMicrobial 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

AbstractVaccines 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

AbstractRNA 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

AbstractIn 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

AbstractA 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.
Promoting Culturally Responsive and Equitable Evaluation With Latinx Immigrants
Authors: Lemos Diana , Garcia David 
Published: July 2020

AbstractCulturally 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

AbstractThis 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

AbstractHolocene 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

AbstractPositron 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

AbstractIn 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.