bluuebunny/crossref_metadata_2025 huggingface dataset:
Suppression of large intraluminal bubble expansion in shock wave lithotripsy without compromising stone comminution: Methodology and in vitro experiments
Authors: Zhong Pei , Zhou Yufeng
Published: July 2002

To reduce the potential of vascular injury without compromising the stone comminution capability of a Dornier HM-3 lithotripter, we have devised a method to suppress intraluminal bubble expansion via in situ pulse superposition. A thin shell ellipsoidal reflector insert was designed and fabricated to fit snugly into the original reflector of an HM-3 lithotripter. The inner surface of the reflector insert shares the same first focus with the original HM-3 reflector, but has its second focus located 5 mm proximal to the generator than that of the HM-3 reflector. With this modification, the original lithotripter shock wave is partitioned into a leading lithotripter pulse (peak positive pressure of 46 MPa and positive pulse duration of 1 μs at 24 kV) and an ensuing second compressive wave of 10 MPa peak pressure and 2 μs pulse duration, separated from each other by about 4 μs. Superposition of the two waves leads to a selective truncation of the trailing tensile component of the lithotripter shock wave, and consequently, a reduction in the maximum bubble expansion up to 41% compared to that produced by the original reflector. The pulse amplitude and −6 dB beam width of the leading lithotripter shock wave from the upgraded reflector at 24 kV are comparable to that produced by the original HM-3 reflector at 20 kV. At the lithotripter focus, while only about 30 shocks are needed to cause a rupture of a blood vessel phantom made of cellulose hollow fiber (i.d.=0.2 mm) using the original HM-3 reflector at 20 kV, no rupture could be produced after 200 shocks using the upgraded reflector at 24 kV. On the other hand, after 100 shocks the upgraded reflector at 24 kV can achieve a stone comminution efficiency of 22%, which is better than the 18% efficiency produced by the original reflector at 20 kV (p=0.043). All together, it has been shown in vitro that the upgraded reflector can produce satisfactory stone comminution while significantly reducing the potential for vessel rupture in shock wave lithotripsy.
Effects of strong sound velocity gradients on propagation of low-frequency impulse sound: Comparison of fast field program predictions and experimental data
Authors: Hole L. R. , Lunde P. , Gjessing Y. T.
Published: July 2002

As part of a large outdoor sound propagation experiment series, propagation of low-frequency impluse sound at ranges from 100 to 1400 m was studied at Haslemoen, Norway in February 1995. Sound sources were charges of 1 and 8 kg C4 explosives. Experiments were carried out in both a uniform forest and above a flat and uniform open field. Extensive meteorological measurements were carried out. Both automatic weather stations mounted in permanent towers and a tethered balloon were employed. The measurements resulted in a manifold set of sound velocity profiles. Occasionally, profiles were pure downwind or upwind, but mostly they were complex, often with large vertical gradients. One conclusion is that one should not uncritically use simple profile parameterizations, e.g., logarithmic, in sound propagation models. A fast field program (FFP), CAPROS, handles the complex sound-speed profiles well, predicting propagation of sound at 8, 16, 32.5, and 63 Hz. In this model, ground is considered a viscoelastic medium. At 63 Hz, the forest seems to cause an excess attenuation. At the lower frequencies, distinct effects of forest are not observed. There is no evidence that FFP predictions are less accurate in periods with high turbulence levels, which is here characterized with dynamical instability. However, variability of meteorological profiles causes predictions to be less accurate. This investigation suggests that it is sufficient to sample atmospheric variables up to 300 m above ground to predict sound propagation at the ranges studied here.
Cubic distortion product otoacoustic emissions in young and aged chinchillas exposed to low-frequency noise
Authors: McFadden Sandra L. , Campo Pierre
Published: July 2002

The aim of this study was to examine susceptibility to noise-induced hearing loss in animals with and without age-related hearing loss (AHL), using cubic distortion product otoacoustic emissions (CDPs) to assess the functional status of the outer hair cell (OHC) system. Subjects were young (⩽3-yr-old) and aged (10- to 15-yr-old) chinchillas. CDP thresholds and input/output (I/O) functions were measured before and after exposure to 95 dB or 106 dB SPL low-frequency noise. The results indicate that (a) aging in the chinchilla is associated with significant elevations of CDP thresholds and depression of CDP I/O functions, (b) noise exposures cause equivalent CDP threshold elevations and amplitude reductions in young animals with normal hearing and older animals with AHL, and (c) CDP threshold and amplitude measures provide information that complements evoked potentials measured from the auditory midbrain.
Acoustic studies comparing Danish vowels, British English vowels, and Danish-accented British English vowels
Authors: Steinlen Anja , Bohn Ocke-Schwen
Published: July 2002

Few studies have examined the production of English vowels by native speakers of languages with vowel inventories as large as, or larger than, English. Danish is such a language, whose vowels are unevenly distributed in the vowel space, with a densely populated upper portion and a sparsely populated lower portion of the vowel space. This paper reports on acoustic comparisons of British English vowels as produced by ten native speakers of British English and of Danish, and of Danish vowels as produced by ten native speakers of Danish. Danish and English vowels were produced in CVC syllables in a variety of consonantal contexts. Acoustic analyses revealed temporal, spectral, and dynamic differences between the vowels produced by the speaker groups. The results of this study suggest that comparisons of vowels across languages, as well as analyses of the productions of non-native speakers, are incomplete and may even be misleading unless the effects of consonantal context are taken into account. The results of this study also provide an interesting test case for Flege’s speech learning model, which makes predictions concerning the learnability of foreign language vowels based on their degree of difference from native language categories.
Significance of Viscosity Measurements in Macroscopic Suspensions of Elongated Particles
Authors: Attanasio A. , Bernini U. , Galloppo P. , Segré G.
Published: July 2002

This paper investigates the conditions whereby it is possible to give an objective value to viscosity measurements of a suspension of artificial rigid fibers. It is shown that, as long as the ratio between the length of the particles and the width of the field of flow is not larger than 13, viscosity measurements carried out with capillary viscometer and with Couette viscometer are equivalent and linearly related with the axial ratio of the particles.
Rheological Properties of Glass Fiber-Reinforced Dough Molding Compounds
Authors: Gandhi K. S. , Burns R.
Published: July 2002

Rheological properties of thermosetting glass fiber-filled Dough Molding Compounds (DMC) are useful in understanding the fiber orientation in moldings caused by flow patterns in the mold as well as in assessing the moldability of the material. A rheometer utilizing the squeeze flow between two parallel circular discs was shown to be successful in characterizing the viscous properties of DMC. The viscometric data indicate that addition of glass fibers makes the DMC slurry more viscous and shear thinning and that the extent of these effects increases with the weight fraction of glass fibers. The length-to-diameter ratio of the fibers was found to be an important variable. At the same volume fraction, glass fibers with a larger length-to-diameter ratio make the DMC more viscous and shear thinning.
The Golden Touch by Light: A Finely Engineered Luminogen Empowering High Photoactivatable and Photodynamic Efficiency for Cancer Phototheranostics
Authors: Chen Xiaohui , Niu Niu , Li Dan , Zhang Zicong , Zhuang Zeyan , Yan Dingyuan , Li Jiangao , Zhao Zujin , Wang Dong , Tang Ben Zhong
Published: December 2022

Photoactivatable agent is a powerful tool in biomedicine studies due to high‐precision spatiotemporal control of light. However, those previously reported agents generally suffer from short wavelength, fluorescence self‐quenching effect, and the lack of photosensitizing property, which severely restrict their practical applications. To address these issues, molecular engineering of 1,4‐dihydropyridine derivatives is conducted to obtain an optimized agent, namely TPA‐DHPy‐Py, which exhibits low oxidation potential, high photoactivation efficiency, and excellent type I/II combined photodynamic activity. Concurrently, its photoactivated counterpart is featured by aggregation‐induced near‐infrared emission and remarkable reactive oxygen species (ROS) production efficiency. Upon photoactivation, TPA‐DHPy‐Py is capable of precisely identifying cancer cells from co‐culturing cancer cells and normal cells without the assistance of any extra targeting units, and in situ monitoring lipid droplets and endoplasmic reticulum alteration under ROS stress, as well as achieving fluorescent visualization of tumor in vivo with supremely high imaging contrast. Furthermore, the unprecedented performance on photodynamic cancer therapy is demonstrated by the significant inhibition of tumor growth. Therefore, the photoactivatable TPA‐DHPy‐Py with dual‐organelle‐targeted and excellent photodynamic activity associated with self‐monitoring ability is highly promising for cancer theranostics in clinical trials.
Enabling Efficient Photocatalytic Hydrogen Evolution via In Situ Loading of Ni Single Atomic Sites on Red Phosphorus Quantum Dots
Authors: Jia Guangri , Sun Mingzi , Wang Ying , Cui Xiaoqiang , Huang Bolong , Yu Jimmy C.
Published: December 2022

Currently, red phosphorus (RP) based catalysts have shown great potential for photocatalysis due to several important intrinsic advantages. The integration of single atomic sites and RP becomes a promising solution, which has rarely been discussed. Herein, a brand‐new type of photocatalyst is proposed by in situ loading Ni single atoms on the P vacancy defects of the RP quantum dots (Ni‐RPQD), achieving the successful attempt of combining single atomic catalyst (SAC), RP, and QDs for the first time. The Ni‐P sites act as electron antennas, which attract the photocarriers to the solid‐liquid interface and activate protons to initiate an efficient hydrogen production process, resulting in a high hydrogen production rate, which is 224 times higher than that of the original RPQD and is also superior to most reported RP‐based photocatalysts and competitive with the non‐noble metal‐based SAC photocatalysts. Theoretical explorations reveal that the atomically dispersed Ni atoms significantly lower the energy barrier for electron transfer during photocatalysis. This results in enhanced adsorption and fast dissociation of water molecules for more efficient H2 generation. This study offers a significant and new direction for future developments of advanced and stable photocatalysts for water splitting.
The Synergistic Activation of Ce‐Doping and CoP/Ni3P Hybrid Interaction for Efficient Water Splitting at Large‐Current‐Density
Authors: Zhang Fan , Wang Xin , Han Weiwei , Qian Yang , Qiu Lingshu , He Yi , Lei Lecheng , Zhang Xingwang
Published: December 2022

The high intermediate (H*, OH*) energy barriers and slow mass/charge transfer increase the overpotential of alkaline water electrolysis at large‐current‐density. Engineering the electronic structure with the morphology of the catalyst to reduce energy barriers and improve mass/charge transportation is effective but remains challenging. Herein, a Ce‐doped CoP nanosheet is hybrid with Ni3P@NF (Ni foam) support to enhance mass/charge transfer, tune energy barriers, and improve water‐splitting kinetics through a synergistic activation. The engineered Ce0.2‐CoP/Ni3P@NF cathode exhibits an ultralow overpotential (η500, η1000) of −185, and −225 mV at −500 and −1000 mA cm−2in 1.0 m KOH, along with an excellent pH‐universality. Impressively, an electrolyzer using the Ce0.2‐CoP/Ni3P@NF cathode can afford 500 mA cm−2at a cell voltage of only 1.775 V and maintain stable electrolysis for 200 h in 25 wt% KOH (50 °C). Characterization and density functional theory calculation further reveal the Ce‐doping and CoP/Ni3P hybrid interaction synergistically downshift d‐band centers (εd = −2.0 eV) of Ce0.2‐CoP/Ni3P to the Fermi level, thereby activate local electronic structure for accelerating H2O dissociation and optimizing Gibbs free energy of hydrogen adsorption (∆GH*).
Light Switching Microprojector Allows Endoscopic In Vivo 3D Imaging of Gastrointestinal Abnormalities
Authors: Yang Sung-Pyo , Kwon Jae-Myeong , Seo Jae-Won , Jun Han Jo , Hwang Kyungmin , Kim Eun-Sun , Jeong Ki-Hun
Published: December 2022

Quantitative in vivo measurement helps physicians determine abnormal tissue size or resection margin accurately. Herein, in vivo 3D imaging of abnormal features during endoscopic operation using a light switching microprojector is reported. The microprojector features rotational offset microlens arrays and a customized illumination fiber bundle fully integrated through a single illumination channel of a clinical endoscope. The illumination channel switches white light into structured laser patterns on demand. The 3D profiles are precisely extracted by calculating the distortion of uniform structured patterns on a target surface. The 3D endoscope allows the precise measurement of the size and volume of polyp phantoms within 7.70% and 13.33% errors, respectively. The experimental results show the accurate measurements of abnormal ex vivo human abnormal tissue and in vivo volume changes in the inflated stomach wall of an anesthetized pig. The microprojector can provide a new opportunity for in vivo 3D endoscopic imaging and biometric applications.
RNF126‐Mediated MRE11 Ubiquitination Activates the DNA Damage Response and Confers Resistance of Triple‐Negative Breast Cancer to Radiotherapy
Authors: Liu Wenjing , Zheng Min , Zhang Rou , Jiang Qiuyun , Du Guangshi , Wu Yingying , Yang Chuanyu , Li Fubing , Li Wei , Wang Luzhen , Wu Jiao , Shi Lei , Li Wenhui , Zhang Kai , Zhou Zhongmei , Liu Rong , Gao Yingzheng , Huang Xinwei , Fan Songqing , Zhi Xu , Jiang Dewei , Chen Ceshi
Published: December 2022

Triple‐negative breast cancer (TNBC) has higher molecular heterogeneity and metastatic potential and the poorest prognosis. Because of limited therapeutics against TNBC, irradiation (IR) therapy is still a common treatment option for patients with lymph nodes or brain metastasis. Thus, it is urgent to develop strategies to enhance the sensitivity of TNBC tumors to low‐dose IR. Here, the authors report that E3 ubiquitin ligase Ring finger protein 126 (RNF126) is important for IR‐induced ATR‐CHK1 pathway activation to enhance DNA damage repair (DDR). Mechanistically, RNF126 physically associates with the MRE11‐RAD50‐NBS1 (MRN) complex and ubiquitinates MRE11 at K339 and K480 to increase its DNA exonuclease activity, subsequent RPA binding, and ATR phosphorylation, promoting sustained DDR in a homologous recombination repair‐prone manner. Accordingly, depletion of RNF126 leads to increased genomic instability and radiation sensitivity in both TNBC cells and mice. Furthermore, it is found that RNF126 expression is induced by IR activating the HER2‐AKT‐NF‐κB pathway and targeting RNF126 expression with dihydroartemisinin significantly improves the sensitivity of TNBC tumors in the brain to IR treatment in vivo. Together, these results reveal that RNF126‐mediated MRE11 ubiquitination is a critical regulator of the DDR, which provides a promising target for improving the sensitivity of TNBC to radiotherapy.
Homemade Solution of NaOD in D2O: Applications in the Field of Stilbene‐d1 Synthesis
Authors: Imai Keisuke , Tomita Naohito , Fujioka Hiroyoshi , Kamiya Mako , Ogasahara Riku , Ban Kazuho , Shimizu Hyoga , Ishimoto Takayoshi , Sajiki Hironao , Akai Shuji , Sawama Yoshinari
Published: December 2022

The development of deuterium‐incorporation method is eagerly desired. A solution of sodium deuteroxide in deuterium oxide (NaOD in D2O) was simply prepared by mixing D2O and t‐BuONa. Subsequently, the t‐BuOD layer, generated under conditions of the salting‐out effect, was separate. The purity (volume of the contaminated t‐BuOD as side‐product) of the homemade NaOD in D2O was evaluated by 1H NMR and Raman analyses. NaOD in D2O was used for the one‐pot synthesis of mono‐deuterated trans‐stilbene (stilbene‐d1) in the aqueous Horner‐Wadsworth‐Emmons reaction. The present method can be widely applied to synthesize the various mono‐deuterated stilbene derivatives with high deuterium content. Additionally, the obtained mono‐deuterated stilbene derivatives could be successfully converted to various deuterated compounds.
Hysteresis‐Free and High‐Sensitivity Strain Sensing of Ionically Conductive Hydrogels
Authors: Song Jiwoo , Mou Chenchen , Balakrishnan Gaurav , Wang Yingqiao , Rajagopalan Mahathy , Schreiner Audrey , Naik Durva , Cohen-Karni Tzahi , Halbreiner M. Scott , Bettinger Christopher J.
Published: December 2022

Hydrogels are promising materials for soft and implantable strain sensors owing to their large compliance (E < 100 kPa) and significant extensibility (ε
max > 500%) compared with other polymer networks. Further, hydrogels can be functionalized to seamlessly integrate with many types of tissues. However, most current methods attempt to imbue additional electronic functionality to structural hydrogel materials by incorporating fillers with orthogonal properties such as electronic or mixed ionic conduction. Although composite strategies may improve performance or facilitate heterogeneous integration with downstream hardware, composites complicate the path for regulatory approval and may compromise the otherwise compelling properties of the underlying structural material. Herein, hydrogel strain sensors composed of genipin‐crosslinked gelatin and dopamine‐functionalized poly(ethylene glycol) for in vivo monitoring of cardiac function are reported. By measuring their impedance only in their resistive regime (>10 kHz), hysteresis is reduced and the resulting gauge factor is increased by ≈50× to 1.02 ± 0.05 and 1.46 ± 0.05 from ≈0.03 to 0.05 for PEG‐Dopa and genipin‐crosslinked gelatin, respectively. Adhesion and in vivo biocompatibility are studied to support implementation of strain sensors for monitoring cardiac output in porcine models. Impedance‐based strain sensing in the kilohertz regime simplifies the piezoresistive behavior of these materials and expands the range of hydrogel‐based strain sensors.
Visualizing the Intermittent Gating of Na+/H+ Antiporters in Single Native Bioluminescent Bacteria**
Authors: Li Yaohua , Li Haoran , Gao Jia , Niu Ben , Wang Huan , Wang Wei
Published: December 2022

While the intermittent gating of ion channels has been well studied for decades, dynamics of the action of secondary transporters, another major pathway for ion transmembrane transports, remains largely unexplored in living cells. Herein, intermittent blinking of the spontaneous bioluminescence (BL) from single native bacteria, P. phosphoreum, was reported, investigated and attributed to the intermittent gating of sodium/proton antiporters (NhaA) between the active and inactive conformations. Each gating event caused the rapid depolarization and recovery of membrane potential within several seconds, accompanying with the apparent BL blinking due to the transient inhibitions on the activity of the respiratory chain. Temperature‐dependent measurements further obtained an activation energy barrier of the conformational change of 20.3 kJ mol−1.
Copper‐Catalyzed Enantioselective C1,N‐Dipolar (3+2) Cycloadditions of 2‐Aminoallyl Cations with Indoles
Authors: Shen Lulu , Zheng Yin , Lin Zitong , Qin Tianzhu , Huang Zhongxing , Zi Weiwei
Published: December 2022

2‐Aminoallyl cations are versatile 1,3‐dipoles that could potentially be used for diverse (3+n) cycloaddition reactions. Despite some preliminary studies, the asymmetric catalytic transformation of these species is still underdeveloped. We herein report a binuclear copper‐catalyzed generation of 2‐aminoallyl cations from ethynyl methylene cyclic carbamates and their enantioselective (3+2) cycloaddition reaction with indoles to construct chiral pyrroloindolines. This transformation features a novel C1,N‐dipolar reactivity for 2‐aminoallyl cations.
Numerical approximations for the dynamics of cosmological scalar fields with a quartic self‐interaction
Authors: Ureña‐López L. Arturo
Published: December 2022

In this paper, I present a new representation of the cosmological equations of motion for a cosmic scalar field endowed with a composite potential, which contains two terms: one quadratic and one quartic, and show that it can be transformed into a suitable dynamical system under a spherical change of variables. I discuss the features of the solutions and the critical points of the new system in the case of a single‐field model, and make a comparison with direct solutions of the Klein‐Gordon equation. Also, the case of rapid field oscillations is considered, together with the proposal to cut them off from the numerical solutions.
Correspondence between resident‐ and staff‐report on the QABF: Do justice‐involved youth agree with residential staff?
Authors: Sheridan Daniel J. , Edgemon Anna Kate , Rapp John T.
Published: December 2022

Residents in juvenile residential treatment facilities (JRTFs) often display various emotional, behavioral, and educational needs. Researchers have recently developed behavioral interventions to increase residents' appropriate behavior such as cooperation with facility staff instructions, accepting feedback from facility staff, and tolerating unpleasant events. However, there is not a generally accepted tool for assessing the operant function of residents' problem behavior in JRTFs. For various logistical reasons, indirect functional assessments may be more appropriate in a JRTF than manipulating either antecedent or consequent events. This study obtained scores on the Questions About Behavior Function (QABF) assessment for 17 residents from two dormitory staff members for each resident. To increase the number of respondents, each resident completed a QABF for their own behavior. Results revealed moderate to high correspondence (i.e., agreement) for highest and lowest potential operant function of problem behavior between combinations of JRTF staff and residents. These preliminary findings suggest additional research with the QABF in JRTFs is warranted.
Hybrid Hydrothermal Carbonization and Ultrasound Technology on Oil Palm Biomass for Hydrochar Production
Authors: Madusari Sylvia , Jamari Saidatul Shima , Nordin Noor Ida Amalina Ahamad , Bindar Yazid , Prakoso Tirto , Restiawaty Elvi , Steven Soen
Published: December 2022

The hybrid hydrothermal carbonization and ultrasound technology (HHTC‐Us) efficiently utilizes the function of both ultrasounds‐assisted and hydrothermal carbonization for hydrochar production. The HHTC‐Us of oil palm residues plays an essential role in hydrochar production. Hydrochar is a carbon‐rich material potentially produced from oil palm biomass, which has gained great interest due to its unique properties. Four main topics were highlighted: the production of crude palm oil and impacted biomass residue generation, properties and potential values of oil palm biomass conversion as hydrochar, hybrid hydrothermal carbonization reaction routes, and processing parameters that affect the HHTC‐Us technology. The review elucidates the promising production process or modification of hydrochar from oil palm biomass residues through hybrid technology. The technology potentially enhanced sustainability, creating challenges and new opportunities.
Novel biotechnological approaches to improving aromas and flavors of legume‐derived food products
Authors: Kryachko Yuriy , Tanaka Takuji , Nickerson Michael T. , Korber Darren R.
Published: December 2022

Background and Objectives

Beany flavor and aroma pertaining to legumes and legume‐derived food products are among the reasons for their limited acceptance by Western consumers. Fermentation has been used for improving qualities of various food sources in traditional cuisines across the globe for millennia. This review is dedicated to novel ideas regarding the improvement of flavor and aroma properties of legumes and legume‐derived products using fermentation and/or enzymatic treatments. Special attention is paid to the utilization of microorganisms capable of cyclodextrin (CD) production.

Findings

Novel genetically engineered and/or immobilized microorganisms, such as Bacillus spp., or enzymes, such as cyclodextrin glycosyl transferases (CGTases), were recently shown to be efficient in helping remove undesirable odor‐/flavor‐active compounds from food products.

Conclusions

Fermentation of legumes/legume‐derived products by CD‐producers is an industrially feasible approach to the production of novel legume‐derived food products with improved odor/flavor properties.

Significance and Novelty

On the basis of the reviewed material, a two‐stage processing of legumes/legume‐derived products, including either acid treatment or fermentation by lactic acid bacteria (LAB) at the first stage to unbind odor‐/flavor‐active compounds from proteins and then, at the second stage, using CD‐producers (primarily Bacillus spp.) to scavenge such compounds with CDs, is proposed.
Selenium‐doped Graphite for Electrochemical Sensing and Adsorption of Hg(II) and Cd(II) Ions
Authors: Maity Sayantan , Deshmukh Sujit , Roy Susanta Sinha , Dhar Basab Bijayi
Published: December 2022

Selenium‐doped Graphite (Se‐DG) has been used for electrochemical (EC) sensing and adsorption of poisonous Hg(II) and Cd(II) ions which can produce acute toxic effects on various organs. Hence, detection and efficient removal of both the metal ions from aquatic sources are very crucial. Herein, square wave anodic stripping voltammetry (SWASV) method was applied for EC detection using Se‐DG coated glassy carbon electrode (GCE) as a working electrode. Corresponding EC responses were observed due to the interaction between the sensing surface and the analytes. Elemental Se (Se0) present in Se‐DG played a crucial role in EC sensing. The limit of detection (LoD) of Hg(II) and Cd(II) were observed to be 4.3 ppb and 1.9 ppb respectively. The limit of quantification (LoQ) were found as ppb 14.3 ppb and 6.3 ppb respectively. Batch method was carried out for adsorption of the same carcinogenic metal ions on the Se‐DG surface. Ultra‐trace concentration of the metal ions was determined in Inductively Coupled Plasma Mass Spectrometry (ICP‐MS). Maximum adsorption capacity (QM) for Hg(II) and Cd(II) were found 210.81 mg g−1 and 205.53 mg g−1 respectively from Langmuir fit. The adsorption process was spontaneous and endothermic and it could be better fitted by a pseudo‐second order rate law, suggesting a chemisorption over physisorption. X‐Ray Photoelectron spectroscopy (XPS) was performed to investigate the binding interaction of different functionalities present in Se‐DG with metal ions.
Probing the Importance of Host Symmetry on Carbohydrate Recognition
Authors: Manick Anne‐Doriane , Li Chunyang , Antonetti Elise , Albalat Muriel , Cotelle Yoann , Nava Paola , Dutasta Jean‐Pierre , Chatelet Bastien , Martinez Alexandre
Published: December 2022

The design of molecular cages with low symmetry could allow for more specific tuning of their properties and better mimic the unsymmetrical and complex environment of protein pockets. However, the added value of lowering symmetry of molecular receptors has been rarely demonstrated. Herein, C3‐ and C1‐symmetrical cages, presenting the same recognition sites, have been synthesized and investigated as hosts for carbohydrate recognition. Structurally related derivatives of glucose, galactose and mannose were found to have greater affinity to the receptor with the lowest symmetry than to their C3‐symmetrical analogue. According to the host cavity modelling, the C1 symmetry receptor exhibits a wider opening than its C3‐symmetrical counterpart, providing easier access and thus promoting guest proximity to binding sites. Moreover, our results show the high stereo‐ and substrate selectivity of the C1 symmetry cage with respect to its C3 counterpart in the recognition of sugars.
Guided Isolation of An Uncommon Cembranoid Orthoester, Sarcotortin A, and Three Skeletal Diverse Terpenoids from the Hainan Soft Coral Sarcophyton tortuosum Based on Molecular Networking Strategy
Authors: Chen Zi‐Hui , Yu Dan‐Dan , Li Cong , Su Ming‐Zhi , Wu Qihao , Zhang Zai‐Yong , Wang Jian‐Rong , Li Jia , Guo Yue‐Wei
Published: December 2022

Applying the emerging molecular networking strategy, an uncommon cembranoid orthoester, sarcotortin A (1), featuring a 3/14/8/5‐fused scaffold, an unusual eunicellane‐type diterpenoid, sarcotorolide A (2), and two new biscembranoids, ximaolides M and N (7 and 8), along with nine known terpenoids 3–6 and 9–13 were isolated from the Hainan soft coral Sarcophyton tortuosum. The structure and absolute configuration of all new compounds were established by a combination of spectroscopic data, X‐ray diffraction analysis, and/or quantum chemical computational approaches. The plausible biogenetic relationship among these skeletally different terpenoids was proposed and discussed. In in vitro bioassay, new compound 7 exhibited a remarkable inhibitory activity against protein tyrosine phosphatases 1B (PTP1B) with the IC50 value of 8.06 μM. In addition, compounds 4 and 10 displayed significant inhibitory effects on lipopolysaccharide (LPS)‐induced inflammatory responses in RAW264.7 macrophages cells with the IC50 values of 19.13 and 16.45 μM, respectively. Compound 9 showed interesting cytotoxicity against H1975, MDA‐MB231, A549, and H1299 cancer cell lines with IC50 values of 31.59, 34.96, 43.87, and 27.93 μM, respectively.
Synthesis and Structure‐Property Relationships in Regioisomeric Alternating Borane‐Terthiophene Polymers
Authors: Alahmadi Abdullah F. , Yin Xiaodong , Lalancette Roger A. , Jäkle Frieder
Published: December 2022

Main‐chain boron‐containing π‐conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene‐borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6‐tri‐tert‐butylphenyl, Mes*; 2,4,6‐tris(trifluoromethyl)phenyl, FMes) examined. Pd2dba3/P(t‐Bu)3‐catalyzed Stille polymerization of arylbis(2‐thienyl)borane and arylbis(3‐thienylborane) with 2,5‐bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI‐TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5‐bis(tri‐n‐butylstannyl)thiophene as comonomer, and Pd2dba3/P(o‐tol)3 as the catalyst at 100 °C. Under these conditions, macrocyclic species with n=3–10 repeating units formed preferentially according to MALDI‐TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow‐green, blue‐green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.
C−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylene
Authors: Witte Robert , Arrowsmith Merle , Lamprecht Anna , Schorr Fabian , Krummenacher Ivo , Braunschweig Holger
Published: December 2022

A cyclic alkyl(amino)carbene (CAAC)‐stabilized dicoordinate aminoborylene is synthesized by the twofold reduction of a [(CAAC)BCl2(TMP)] (TMP=2,6‐tetramethylpiperidyl) precursor. NMR‐spectroscopic, X‐ray crystallographic and computational analyses confirm the cumulenic nature of the central C=B=N moiety. Irradiation of [(CAAC)B(TMP)] (2) resulted in an intramolecular C−C bond activation, leading to a doubly‐fused C10BN heterocycle, while the reaction with acetonitrile resulted in an aryl migration from the CAAC to the acetonitrile nitrogen atom, concomitant with tautomerization of the latter to a boron‐bound allylamino ligand. One‐electron oxidation of2with CuX (X=Cl, Br) afforded the corresponding amino(halo)boryl radicals, which were characterized by EPR spectroscopy and DFT calculations. Placing2under an atmosphere of CO afforded the tricoordinate (CAAC,CO)‐stabilized aminoborylene. Finally, the twofold oxidation of2with chalcogens led, in the case of N2O and sulfur, to the splitting of the B−CCAACbond and formation of the 2,4‐diamino‐1,3,2,4‐dichalcogenadiboretanes and CAAC‐chalcogen adducts, whereas with selenium a monomeric boraselenone was isolated, which showed some degree of B−Se multiple bonding.
Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from PdII to NiII in a Face‐Centered FeII8MII6 Cubic Cage**
Authors: Min Hyunsung , Craze Alexander R. , Wallis Matthew J. , Tokunaga Ryuya , Taira Takahiro , Hirai Yutaka , Bhadbhade Mohan M. , Fanna Daniel J. , Marjo Christopher E. , Hayami Shinya , Lindoy Leonard F. , Li Feng
Published: December 2022

Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in next‐generation molecular transport and catalysis. Previous investigations of cubic cage [Fe8Pd6L8]28+ constructed using semi‐rigid metalloligands, found that FeII centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X‐ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter‐ and intramolecular interactions associated with SCO in the NiII analogue, 1 ([Fe8Ni6L8(CH3CN)12]28+). The distorted octahedral coordination environment, as well as the occupation of the CH3CN in the NiII axial positions of 1, prevented close packing of cages observed in the PdII analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.
A conversation with Nancy Reid
Authors: Craiu Radu V. , Yi Grace Y.
Published: December 2022

Nancy Reid was born in September 1952 in Niagara Falls, Canada. She graduated from the University of Waterloo with a Bachelor in Mathematics and a Major in Statistics in 1974. She studied statistics at the University of British Columbia (UBC) where she obtained a Master's in Applied Mathematics in 1976, and at Stanford University where she graduated with a PhD in Statistics in 1979. After spending one year at Imperial College London visiting Sir David Cox, she joined UBC as an Assistant Professor in the Department of Mathematics, and in 1986 she moved to the University of Toronto as a faculty member in the Department of Statistics (now Statistical Sciences) where she has been ever since including serving as Chair between 1997 and 2002. At the time of writing, Nancy has authored over 100 papers and 5 books, including seminal developments in conditional inference, higher‐order asymptotics, composite likelihood, and Bayesian inference. Her outstanding contributions to statistics have been recognized nationally and internationally with many awards, including the President's Award of the Committee of Presidents of Statistical Societies (COPSS), the Gold Medal awarded by the Statistical Society of Canada (SSC), and being elected Foreign Associate of the National Academy of Sciences. In 2017, the International Statistical Review published Nancy's conversation with Ana Maria Staicu [Staicu, A. M. (2017). Interview with Nancy Reid. International Statistical Review, 85(3), 381‐403.], which had a biographical emphasis. Since then, Nancy has continued to support the discipline of statistics in important ways, such as by serving as Director of the Canadian Statistical Sciences Institute (CANSSI) (2015–2019) and Co‐chair of the Institute of Mathematical Statistics' Committee on Ethics (2018–2020). Her research activity continues to be celebrated with important awards such as Fellowship of the Royal Society of London (2018), the inaugural Hollander Distinguished Lectureship at Florida State University (2020), the Distinguished Achievement Award (and Lectureship) from COPSS (2022), and the Guy Medal in Gold from the Royal Statistical Society (2022). In May 2022, the Department of Statistical Sciences at the University of Toronto, in collaboration with CANSSI and the SSC, organized a one‐day conference, “Statistics at Its Best”, in honour of Nancy's 70th birthday. This conversation took place in Toronto around the time of the event. Its focus is on Nancy's views on building a career in statistics, and the challenges and opportunities statisticians encounter within the rapidly evolving data science ecosystem.
Lobar versus sublobar resection for atypical lung carcinoid: An analysis from the National Cancer Database
Authors: Ernani Vinicius , Appiah Adams Kusi , Rodriguez Daniel , Kusne Yael , Beamer Staci E. , Ravanbakhsh Samine , Jaroszewski Dawn , Reck dos Santos Pedro , Sio Terence T. , Yu Nathan , Yang Ping , Schild Steven , D’Cunha Jonathan
Published: December 2022

Background

There is a knowledge gap regarding lobar versus sublobar resection for atypical carcinoid (AC) of the lung. As such, the authors sought to understand and analyze the outcomes of sublobar resection versus lobectomy in this patient population.

Methods

A retrospective analysis using the National Cancer Database was performed to compare overall survival (OS) between patients treated with lobectomy and patients treated with sublobar resection for AC of the lung between the years 2004 and 2016. Patient characteristics were compared with χ2 tests. The Kaplan–Meier method was used to estimate OS distributions, and the log‐rank test was used to compare distributions by treatment strategy. A multivariable Cox regression model was used to assess associations between the treatment strategy and OS. A propensity score matching method was also implemented to further eliminate treatment selection bias in the study sample.

Results

The database identified 669 patients with T1–T4 and N0–N3 lung ACs that were surgically resected. Unadjusted Kaplan–Meier survival curves did not demonstrate an OS difference between lobectomy and sublobar resection (p = .094). After propensity score matching, curves demonstrated a numerical improvement in OS with lobectomy; however, it was not statistically significant (p = .5). In a subgroup analysis, lobectomy and node‐negative disease were associated with the best OS, whereas sublobar resection and node‐positive disease were associated with the worst OS (p < .0001). Nodal involvement was associated with worse survival, regardless of surgical treatment (p < .0001).

Conclusions

In patients with T1–T4 and N0–N3 ACs of the lung, lobectomy was not associated with an improvement in OS in comparison with sublobar resection.
ZrN6‐Doped Graphene for Ammonia Synthesis: A Density Functional Theory Study
Authors: Wu Jing , Yang Lei , Liu Xin , Zhang Ze , Liu Shanping , Xiao Beibei
Published: December 2022

Considering the pivotal role of ammonia in the modern chemical industry, designing effective catalysts for the N2‐to‐NH3 conversion stimulates great research enthusiasms. In this work, by means of density functional theory calculations, we systematically investigated the electrocatalysis of six‐coordinated transition metal atom anchored graphene for nitrogen fixation. The free energy analysis shows that the ZrN6 configuration has a good activity toward ammonia synthesis under overpotential of 0.51 V. According to the electron transfer analysis, ZrN6 site plays a bridging role in charge transfer between the functional graphene and the reactant. Furthermore, the presence of N6 coordination increases the electron accumulation on the NNHx intermediates, which weakens the intermolecular N−N bond, reducing the thermodynamic barrier of protonation process. This work provides a basic understanding of the interaction between transition metal and the adjacent coordination in tuning the reactivity.
Facilitating Next‐Generation Pre‐Exposure Prophylaxis Clinical Trials Using HIV Recent Infection Assays: A Consensus Statement from the Forum HIV Prevention Trial Design Project
Authors: Parkin Neil , Gao Fei , Grebe Eduard , Cutrell Amy , Das Moupali , Donnell Deborah , Duerr Ann , Glidden David V. , Hughes James P. , Murray Jeffrey , Robertson Michael N. , Zinserling Joerg , Lau Joseph , Miller Veronica ,   for the Forum for Collaborative Research Recency Assay Working Group
Published: December 2022

Standard‐of‐care HIV pre‐exposure prophylaxis (PrEP) is highly efficacious, but uptake of and persistence on a daily oral pill is low in many settings. Evaluation of alternate PrEP products will require innovation to avoid the unpractically large sample sizes in noninferiority trials. We propose estimating HIV incidence in people not on PrEP as an external counterfactual to which on‐PrEP incidence in trial subjects can be compared. HIV recent infection testing algorithms (RITAs), such as the limiting antigen avidity assay plus viral load used on specimens from untreated HIV positive people identified during screening, is one possible approach. Its feasibility is partly dependent on the sample size needed to ensure adequate power, which is impacted by RITA performance, the number of recent infections identified, the expected efficacy of the intervention, and other factors. Screening sample sizes to support detection of an 80% reduction in incidence for 3 key populations are more modest, and comparable to the number of participants in recent phase III PrEP trials. Sample sizes would be significantly larger in populations with lower incidence, where the false recency rate is higher or if PrEP efficacy is expected to be lower. Our proposed counterfactual approach appears to be feasible, offers high statistical power, and is nearly contemporaneous with the on‐PrEP population. It will be important to monitor the performance of this approach during new product development for HIV prevention. If successful, it could be a model for preventive HIV vaccines and prevention of other infectious diseases.
Efficacy of power‐driven interdental cleaning tools: A systematic review and meta‐analysis
Authors: Edlund Pia , Bertl Kristina , Pandis Nikolaos , Stavropoulos Andreas
Published: December 2022

Objectives

To summarize the available evidence on the efficacy of power‐driven interdental cleaning tools (PDICTs) as an adjunct to tooth brushing compared to tooth brushing alone or tooth brushing combined with any other non‐PDICT in terms of interproximal plaque and gingival bleeding reduction in gingivitis patients.

Material and Methods

A systematic literature search was performed in three databases until March 20, 2022 with the following main eligibility criteria: (1) randomized controlled clinical trials (RCTs) with (2) at least 28 days of follow‐up in (3) gingivitis patients. Interproximal plaque and bleeding values were defined as the primary outcome variables and used for pair‐wise meta‐analyses.

Results

Sixteen RCTs were identified including data from 1258 participants at the final evaluation. Eight studies each investigated the effect of either a liquid‐based or mechanical PDICT; one of these studies tested additionally a combined liquid‐based and mechanical PDICT. Tooth brushing combined with a liquid‐based PDICT compared to tooth brushing alone did not result in better interproximal plaque values but in significantly lower interproximal bleeding values. Tooth brushing combined with either a liquid‐based PDICT or with a mechanical PDICT compared to tooth brushing and flossing achieved comparable interproximal plaque and bleeding values. The majority of studies reporting on patient compliance/preference favored the use of a PDICT, and except for a single study, which was reporting soft tissue trauma in two subjects from improper use of a mechanical PDICT, none of the studies reported adverse events.

Conclusions

Daily use of PDICT as an adjunct to tooth brushing significantly reduces interproximal bleeding. This effect appears comparable to that of flossing, while PDICT may achieve higher patient acceptance/compliance.
Diffusional Features of a Lithium‐Sulfur Battery Exploiting Highly Microporous Activated Carbon
Authors: Lama Fernando Luna , Marangon Vittorio , Caballero Álvaro , Morales Julián , Hassoun Jusef
Published: December 2022

Diffusion processes at the electrode/electrolyte interphase drives the performance of lithium‐sulfur batteries, and activated carbon (AC) can remarkably vehicle ions and polysulfide species throughout the two‐side liquid/solid region of the interphase. We reveal original findings such as the values of the diffusion coefficient at various states of charge of a Li−S battery using a highly porous AC, its notable dependence on the adopted techniques, and the correlation of the diffusion trend with the reaction mechanism. X‐ray photoelectron spectroscopy (XPS) and X‐ray energy dispersive spectroscopy (EDS) are used to identify in the carbon derived from bioresidues heteroatoms such as N, S, O and P, which can increase the polarity of the C framework. The transport properties are measured by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic intermittent titration technique (GITT). The study reveals Li+‐diffusion coefficient (DLi+) depending on the technique, and values correlated with the cell state of charge. EIS, CV, and GITT yield a DLi+ within 10−7–10−8 cm2 s−1, 10−8–10−9 cm2 s−1, and 10−6–10−12 cm2 s−1, respectively, dropping down at the fully discharged state and increasing upon charge. GITT allows the evaluation of DLi+ during the process and evidences the formation of low‐conducting media upon discharge. The sulfur composite delivers in a Li‐cell a specific capacity ranging from 1300 mAh g−1 at 0.1 C to 700 mAh g−1 at 2C with a S loading of 2 mg cm−2, and from 1000 to 800 mAh g−1 at 0.2C when the S loading is raised to 6 mg cm−2.