bluuebunny/crossref_metadata_2025 huggingface dataset:
Multiple Emission of Phosphonium Fluorophores Harnessed by the Pathways of Photoinduced Counterion Migration
Authors: Belyaev Andrey , Su Bo‐Kang , Cheng Yu‐Hsuan , Liu Zong‐Ying , Khan Nasrulla Majid , Karttunen Antti J. , Chou Pi‐Tai , Koshevoy Igor O.
Published: February 2022

In the emerging field of intramolecular charge transfer induced counterion migration, we report the new insights into photophysical features of luminescent donor–acceptor phosphonium dyes (D−π−)nA+[X−] (π=−(C6H4)x−). The unique connectivity of the phosphorus atom affords multipolar molecules with a variable number of arms and the electronic properties of the acceptor group. In the ion‐paired form, the transition from dipolar to quadrupolar configuration enhances the low energy migration‐induced band by providing the additional pathways for anion motion. The multipolar architecture, adjustable lengths of the π‐spacers and the nature of counterions allow for efficient tuning of the emission and achieving nearly pure white light with quantum yields around 30 %. The methyl substituent at the phosphorus atom reduces the rate of ion migration and suppresses the red shifted bands, simultaneously improving total emission intensity. The results unveil the harnessing of the multiple emission of phosphonium fluorophores by anion migration via structure and branching of donor–acceptor arms.
Synthesis of a π‐Extended Azacorannulenophane Enabled by Strain‐Induced 1,3‐Dipolar Cycloaddition
Authors: Zhang Xinjiang , Mackinnon Marc R. , Bodwell Graham J. , Ito Shingo
Published: February 2022

The first example of a cyclophane bearing a nitrogen‐containing buckybowl was synthesized via sequential 1,3‐dipolar cycloaddition and palladium‐catalyzed intramolecular cyclization. The key to the successful synthesis is the strain‐induced 1,3‐dipolar cycloaddition of a polycyclic aromatic azomethine ylide to theK‐region of [7](2,7)pyrenophane. The resulting π‐extended azacorannulenophane exhibits intriguing structural and physical properties, including unique variation of bowl depth, extraordinarily high‐field chemical shifts in its1H NMR spectrum, a decreased HOMO–LUMO gap, and a red shift in the absorption/emission spectrum, when compared to those of the parent azacorannulene. These characteristics are derived from both the π‐extension to the polycyclic aromatic system in the cyclophane structure and the increased curvature enforced by the seven‐carbon aliphatic chain.
From Structural Design to Functional Construction: Amine Molecules in High‐Performance Formamidinium‐Based Perovskite Solar Cells
Authors: Fu Chunpeng , Gu Zhenkun , Tang Yan , Xiao Qian , Zhang Shasha , Zhang Yiqiang , Song Yanlin
Published: February 2022

Formamidinium (FA) based perovskites are considered as one of the most promising light‐absorbing perovskite materials owing to their narrower band gap and better thermal stability compared to conventional methylammonium‐based perovskites. Constant improvement by using various additives stimulates the potential application of these perovskites. Amine molecules with different structures have been widely used as typical additives in FA‐based perovskite solar cells, and decent performances have been achieved. Thus, a systematic review focusing on structural regulation and functional construction of amines in FA‐based perovskites is of significance. Herein, we analyze the construction mechanism of different structural amines on the functional perovskite crystals. The influence of amine molecules on specific perovskite properties including defect conditions, charge transfer, and moisture resistance are evaluated. Finally, we summarize the design rules of amine molecules for the application in high‐performance FA‐based perovskites and propose directions for the future development of additive molecules.
A Calix[3]acridan‐Based Host–Guest Cocrystal Exhibiting Efficient Thermally Activated Delayed Fluorescence
Authors: Zhou He‐Ye , Zhang Da‐Wei , Li Meng , Chen Chuan‐Feng
Published: February 2022

A supramolecular strategy to construct thermally activated delayed fluorescence (TADF) materials through host–guest charge transfer interactions was proposed. Consequently, a new class of macrocycle namely calix[3]acridan was conveniently synthesized in 90 % yield. The host–guest cocrystal formed by calix[3]acridan and 1,2‐dicyanobenzene exhibited efficient TADF properties due to intense intermolecular charge transfer interactions. Moreover, the spatially separated highest occupied molecular orbital and lowest unoccupied molecular orbital resulted in a very small singlet–triplet energy gap of 0.014 eV and hence guaranteed an efficient reverse intersystem crossing for TADF. Especially, a high photoluminescence quantum yield of 70 % was achieved, and it represents the highest value among the reported intermolecular donor–acceptor TADF materials.
Elektrochemische Carborankäfig‐Aktivierung
Authors: Yang Long , Zhang Zi‐Jing , Bongsuiru Jei Becky , Ackermann Lutz
Published: February 2022

Carborane sind Bor‐Kohlenstoff‐Molekülcluster, welche einzigartige Eigenschaften aufweisen, wie ihre ikosaedrische Geometrie, einen hohen Bor‐Anteil und eine dreidimensional delokalisierte Aromatizität. Diese machen Carborane zu wertvollen Bausteinen in verschiedenen Anwendungsbereichen, wie supramolekularem Design, Nanomaterialien, Optoelektronik, Bor‐Neutroneneinfangtherapeutika (BNCT) und metallorganischer sowie Koordinationschemie. Trotz weitreichender Fortschritte auf diesem Forschungsgebiet werden stöchiometrische Mengen chemischer Redox‐Reagenzien weiterhin für die oxidative Aktivierung der Carborankäfige benötigt. In diesem Kontext ist die elektrochemische Synthese eine vielversprechende und nachhaltige Alternative. In den vergangenen Jahren konnte erheblicher Fortschritt in der elektrochemischen Käfig‐Funktionalisierung an Carboranen erzielt werden, welcher hier zusammengefasst wurde. Wir erwarten, dass die Elektrokatalyse innerhalb der aktuellen Renaissance der Carboran‐Elektrochemie einen immer stärkeren Impuls geben wird.
Hierarchical Assembly of Coordination Macromolecules with Atypical Geometries: Gd44Co28 Crown and Gd95Co60 Cage
Authors: Du Ming‐Hao , Wang Dong‐Hui , Wu Ling‐Wei , Jiang Lin‐Peng , Li Jun‐Ping , Long La‐Sheng , Zheng Lan‐Sun , Kong Xiang‐Jian
Published: February 2022

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously.
Ceria‐Supported Gold Nanoparticles as a Superior Catalyst for Nitrous Oxide Production via Ammonia Oxidation
Authors: Tang Zhenchen , Surin Ivan , Rasmussen Asbjörn , Krumeich Frank , Kondratenko Evgenii V. , Kondratenko Vita A. , Pérez‐Ramírez Javier
Published: February 2022

The production of nitrous oxide, N2O, via NH3 oxidation is not on a practical scale due to the lack of a suitable catalyst. Instead, it is produced via thermal decomposition of NH4NO3, rendering N2O too costly and limiting its prospective uses. Herein, we report CeO2‐supported Au nanoparticles (2–3 nm) as a highly selective catalyst for low‐temperature NH3 oxidation to N2O, exhibiting two orders of magnitude higher space–time yield than the state‐of‐the‐art Mn−Bi/α‐Al2O3 and remarkable stability over 70 h on stream. The reaction proceeds via a Mars–van Krevelen mechanism, with the density of interfacial Auδ+ species and the oxygen storage capacity of CeO2 identified as the key performance descriptors. The latter could be enhanced by cobalt doping, improving the catalytic activity and setting a new benchmark for N2O productivity. These findings establish NH3 oxidation as an efficient process for N2O manufacture and facilitate its broader utilization in selective oxidations.
Nickel‐Catalyzed Intermolecular Asymmetric Addition of Aryl Iodides across Aldehydes
Authors: Zhu Ziqi , Xiao Jieshuai , Li Mingjie , Shi Zhuangzhi
Published: February 2022

Enantioenriched alcohols comprise much of the framework of organic molecules. Here, we first report that chiral nickel complexes can catalyze the intermolecular enantioselective addition of aryl iodides across aldehydes to provide diverse optically active secondary alcohols using zinc metal as the reducing agent. This method shows a broad substrate scope under mild reaction conditions and precludes the traditional strategy through the pre‐generation of organometallic reagents. Mechanistic studies indicate that an in situ formed arylnickel, instead of an arylzinc, adds efficiently to aldehydes, forming a new C−C bond and a chiral nickel alkoxide that may be turned over by zinc powder.
Linker Molecules Convert Commercial Fluorophores into Tailored Functional Probes during Biolabelling
Authors: Zhang Lei , Isselstein Michael , Köhler Jens , Eleftheriadis Nikolaos , Huisjes Nadia M. , Guirao‐Ortiz Miguel , Narducci Alessandra , Smit Jochem H. , Stoffels Janko , Harz Hartmann , Leonhardt Heinrich , Herrmann Andreas , Cordes Thorben
Published: February 2022

Many life‐science techniques and assays rely on selective labeling of biological target structures with commercial fluorophores that have specific yet invariant properties. Consequently, a fluorophore (or dye) is only useful for a limited range of applications, e.g., as a label for cellular compartments, super‐resolution imaging, DNA sequencing or for a specific biomedical assay. Modifications of fluorophores with the goal to alter their bioconjugation chemistry, photophysical or functional properties typically require complex synthesis schemes. We here introduce a general strategy that allows to customize these properties during biolabelling with the goal to introduce the fluorophore in the last step of biolabelling. For this, we present the design and synthesis of ‘linker’ compounds, that bridge biotarget, fluorophore and a functional moiety via well‐established labeling protocols. Linker molecules were synthesized via the Ugi four‐component reaction (Ugi‐4CR) which facilitates a modular design of linkers with diverse functional properties and bioconjugation‐ and fluorophore attachment moieties. To demonstrate the possibilities of different linkers experimentally, we characterized the ability of commercial fluorophores from the classes of cyanines, rhodamines, carbopyronines and silicon‐rhodamines to become functional labels on different biological targets in vitro and in vivo via thiol‐maleimide chemistry. With our strategy, we showed that the same commercial dye can become a photostable self‐healing dye or a sensor for bivalent ions subject to the linker used. Finally, we quantified the photophysical performance of different self‐healing linker–fluorophore conjugates and demonstrated their applications in super‐resolution imaging and single‐molecule spectroscopy.
A General Concurrent Template Strategy for Ordered Mesoporous Intermetallic Nanoparticles with Controllable Catalytic Performance
Authors: Lv Hao , Qin Huaiyu , Ariga Katsuhiko , Yamauchi Yusuke , Liu Ben
Published: February 2022

We report a general concurrent template strategy for precise synthesis of mesoporous Pt‐/Pd‐based intermetallic nanoparticles with desired morphology and ordered mesostructure. The concurrent template not only supplies a mesoporous metal seed for re‐crystallization growth of atomically ordered intermetallic phases with unique atomic stoichiometry but also provides a nanoconfinement environment for nanocasting synthesis of mesoporous nanoparticles with ordered mesostructure and rhombic dodecahedral morphology under elevated temperature. Using the selective hydrogenation of 3‐nitrophenylacetylene as a proof‐of‐concept catalytic reaction, mesoporous intermetallic PtSn nanoparticles exhibited remarkably controllable intermetallic phase‐dependent catalytic selectivity and excellent catalytic stability. This work provides a very powerful strategy for precise preparation of ordered mesoporous intermetallic nanocrystals for application in selective catalysis and fuel cell electrocatalysis.
Active Mechanical Threading by a Molecular Motor**
Authors: Bach Nicolai N. , Josef Verena , Maid Harald , Dube Henry
Published: February 2022

Molecular motors transform external energy input into directional motions and offer exquisite precision for nano‐scale manipulations. To make full use of molecular motor capacities, their directional motions need to be transmitted and used for powering downstream molecular events. Here we present a macrocyclic molecular motor structure able to perform repetitive molecular threading of a flexible tetraethylene glycol chain through the macrocycle. This mechanical threading event is actively powered by the motor and leads to a direct translation of the unidirectional motor rotation into unidirectional translation motion (chain versus ring). The mechanism of the active mechanical threading is elucidated and the actual threading step is identified as a combined helix inversion and threading event. The established molecular machine function resembles the crucial step of macroscopic weaving or sewing processes and therefore offers a first entry point to a “molecular knitting” counterpart.
Step‐by‐step protocol for the isolation and transient transformation of hornwort protoplasts
Authors: Neubauer Anna , Ruaud Stéphanie , Waller Manuel , Frangedakis Eftychios , Li Fay‐Wei , Nötzold Svenja I. , Wicke Susann , Bailly Aurélien , Szövényi Péter
Published: February 2022

Premise

A detailed protocol for the protoplast transformation of hornwort tissue is not yet available, limiting molecular biological investigations of these plants and comparative analyses with other bryophytes, which display a gametophyte‐dominant life cycle and are critical to understanding the evolution of key land plant traits.

Methods and Results

We describe a detailed protocol to isolate and transiently transform protoplasts of the model hornwort Anthoceros agrestis. The digestion of liquid cultures with Driselase yields a high number of viable protoplasts suitable for polyethylene glycol (PEG)‐mediated transformation. We also report early signs of protoplast regeneration, such as chloroplast division and cell wall reconstitution.

Conclusions

This protocol represents a straightforward method for isolating and transforming A. agrestis protoplasts that is less laborious than previously described approaches. In combination with the recently developed stable genome transformation technique, this work further expands the prospects of functional studies in this model hornwort.
Synthesis of azulenolactones through sequential C(2)‐bromoarylation and intramolecular CO bond formation from azulene‐1‐carboxylic acids and di(2‐bromoaryl)iodonium salts in one pot
Authors: Maeng Chanyoung , Lee Phil Ho
Published: February 2022

Sequential C(2)‐bromoarylation reaction and intramolecular CO bond formation from azulene‐1‐carboxylic acids and di(2‐bromoaryl)iodonium salts produced azulenolactones in one pot. The sequential reaction proceeded smoothly through the copper(I)‐mediated cyclization of 2‐(2‐bromoaryl)azulene‐1‐carboxylic acids derived from the regioselective iridium(III)‐catalyzed C(2)‐bromoarylation reaction without decarboxylation.
Engineering Formaldehyde Dehydrogenase from Pseudomonas putida to Favor Nicotinamide Cytosine Dinucleotide
Authors: Wang Junting , Guo Xiaojia , Wan Li , Liu Yuxue , Xue Haizhao , Zhao Zongbao K.
Published: February 2022

The enzyme formaldehyde dehydrogenase (FalDH) from Pseudomonas putida is of particular interest for biotechnological applications as it catalyzes the oxidation of formaldehyde independent of glutathione. However, the consumption of a stoichiometric amount of nicotinamide adenine dinucleotide (NAD) can be challenging at the metabolic level as this may affect many other NAD‐linked processes. A potential solution is to engineer FalDH to utilize non‐natural cofactors. Here we devised FalDH variants to favor nicotinamide cytosine dinucleotide (NCD) by structure‐guided modification of the binding pocket for the adenine moiety of NAD. Several mutants were obtained and the best one FalDH 9B2 had over 150‐fold higher preference for NCD than NAD. Molecular docking analysis indicated that the cofactor binding pocket shrunk to better fit NCD, a smaller‐sized cofactor. FalDH 9B2 together with other NCD‐linked enzymes offer opportunities to assemble orthogonal pathways for biological conversion of C1 molecules.
Treatment‐induced neuropathy of diabetes in an adolescent with rapid reduction in HbA1c and weight loss: Persistent neuropathic findings at follow‐up after 1.5 years
Authors: Rasmussen Vinni Faber , Thrysøe Mathilde , Tankisi Hatice , Karlsson Páll , Vestergaard Esben Thyssen , Kristensen Kurt , Nyengaard Jens Randel , Krogh Klaus , Brock Christina , Terkelsen Astrid Juhl
Published: February 2022

Treatment‐induced neuropathy of diabetes (TIND) is a condition occurring within weeks after a rapid decline in blood glucose. This case report illustrates consequences in an adolescent with TIND. Gold standard methods diagnosing large fiber, small fiber, and autonomic neuropathy were abnormal at 1.5 years of follow‐up. Awareness of TIND is important.
Unilateral adrenal infarction in pregnancy with associated acute hypoadrenalism and subsequent spontaneous biochemical and radiological resolution
Authors: Shah Najeeb , Deshmukh Harshal , Akbar Muhammad Jawaid , Saeed Yamna , Akbar Shahzad , Malik Shah , Allan Belinda
Published: February 2022

Adrenal infarction is a rare cause of abdominal pain during pregnancy, and if missed, it can result in devastating clinical consequences for the mother and the child. The authors report a case of a young female who presented with severe abdominal pain and nausea. The biochemistry showed raised inflammatory markers and significant lactic acidosis. As the cause of the symptoms was not clear and the patient continued to deteriorate, a contrast‐enhanced CT abdomen and pelvis was done which was suggestive of an acute left adrenal infarction. Subsequently, the patient was confirmed to have biochemical hypoadrenalism and required replacement doses of hydrocortisone until recovery of the adrenal glucocorticoid reserve and anticoagulation for the duration of pregnancy. We discuss the workup including diagnostic imaging, follow‐up, and considerations for future pregnancies in this case.
Combined Effect of Palladium Catalyst and the Alcohol to Promote the Uncommon Bis‐Alkoxycarbonylation of Allylic Substrates
Authors: Olivieri Diego , Tarroni Riccardo , Della Ca' Nicola , Mancuso Raffaella , Gabriele Bartolo , Spadoni Gilberto , Carfagna Carla
Published: February 2022

A chemoselective method for the carbonylation of allylic substrates CH2=CHCH2X (X=OAc, OC(O)CH2CN, OPh, OEt, OC(O)OPh, OC(O)OiBu, N(H)C(O)Ph, N(Ph)C(O)Ph, N(H)Boc, N(Ph)Boc, Ph, CO2Bn, CN), leading to alkyl succinates with preservation of the X group, under Pd(II)‐catalyzed oxidative carbonylation conditions, has been developed. Our method shows a completely different inverse chemoselectivity with respect to the “classical” substitutive carbonylation of the allyl compounds, which is known to provide β,γ‐unsaturated carbonyl derivatives through the formation of a π‐allylpalladium intermediate. An accurate study, carried out using allyl acetate as model substrate, allowed to maximize the selectivity in the envisioned 2‐CH2X substituted succinates. The best catalyst is generated in situ by mixing Pd(TFA)2 (TFA=trifluoroacetate) and the N,N′‐di(anthracen‐9‐yl)butane‐2,3‐diimine ligand. p‐Benzoquinone was used as oxidant in presence of benzyl alcohol, which acts as a nucleophile and as a solvent, under 4 bar of CO at 20 °C. A combined effect of the ligand and the nucleophile, rationalized through DFT calculations, has been observed both in promoting the bis‐alkoxycarbonylation process and in preventing π‐allylpalladium‐mediated side reactions, allowing the attainment of succinate derivatives with moderate to good yields.
The Spin Modulation Stimulated Efficient Electrocatalytic Oxygen Evolution Reaction over LaCoO3 Perovskite
Authors: Zhou Fangping , Zhao Zhao , Xu Ming , Wang Ting , Yang Huiru , Wang Rong , Wang Jiahui , Li Haibo , Feng Ming
Published: February 2022

Perovskite is a promising non‐noble catalyst and has been widely investigated for the electrochemical oxygen evolution reaction (OER). However, there is still serious lack of valid approaches to further enhance their catalytic performance. Herein, we propose a spin state modulation strategy to improve the OER electrocatalytic activity of typical perovskite material of LaCoO3. Specifically, the electronic configuration transition was realized by a simple high temperature thermal reduction process. M‐H hysteresis loop results reveal that the reduction treatment can produce more unpaired electrons in 3d orbit by promoting the electron transitions of Co from low spin state to high spin state, and thus lead to the increase of the spin polarization. Electrochemical measurements show that the catalytic performance of LaCoO3 is strongly dependent on its electronic configuration. With the optimized reduction treatment, the overpotential for the OER process in 0.5 M KOH electrolyte solution at 10 mA cm−2 current density was 396 mV, significantly lower than that of the original state. Furthermore, it can mediate efficient OER with an overpotential of 383 mV under an external magnetic field, which is attributed to the appropriate electron filling. Our results show that electron spin state regulation is a new way to boost the OER electrocatalytic activity.
Efficient Photocatalytic Carbonyl Alkylative Amination Enabled by Titanium‐Dioxide‐Mediated Decarboxylation
Authors: Xu Mei , Hua Ying , Fu Xin , Liu Jie
Published: February 2022

Herein, a heterogeneous carbonyl alkylative amination reaction that proceeds by photoredox catalysis has been developed. The use of nano titanium dioxide (TiO2, 25 nm) as photocatalyst allows efficient synthesis of diverse amines in good to excellent yields. Mechanistic studies reveal a single‐electron‐transfer mechanism involving the photoexcitation of TiO2 to generate alkyl radicals from carboxylic acids decarboxylation. This protocol highlights the utility of using heterogeneous semiconductor photocatalysts to promote a practical and general synthesis of complex amines from readily available feedstocks.
Tuning Diradical Properties of Boron‐Containing π‐Systems by Structural Isomerism
Authors: Tian Xinyu , Guo Jiaxiang , Sun Wenting , Yuan Liuzhong , Dou Chuandong , Wang Yue
Published: February 2022

Tuning diradical character is an important topic for organic diradicaloids. Herein, we report the precise borylation enabling structural isomerism as an effective strategy to modulate diradical character and thereby properties of organic diradicaloids. We synthesized a new B‐containing polycyclic hydrocarbon that has the indeno[1,2‐b]fluorene π‐skeleton with the β‐carbons bonding to two boron atoms. Detailed theoretical and experimental results show that this bonding pattern leads to its distinctive electronic structures and properties in comparison to that of its isomeric molecule. This molecule has the efficient conjugation between boron atoms and π‐skeleton, resulting in downshifted LUMO and HOMO levels. Moreover, it exhibits smaller diradical character and thereby inhibited diradical properties, such as significantly blue‐shifted light absorption, larger energy bandgap and weak para‐magnetic resonance. Notably, this B‐containing polycyclic hydrocarbon possesses much stronger Lewis acidity and its Lewis acid‐base adducts display enhanced diradical character, demonstrating the positive effects of Lewis coordination on modulating diradical performance.
Disordered Low Molecular Weight Spiropyran Exhibiting Photoregulated Adhesion Ability
Authors: Zhang Lei , Deng Yawen , Xie Congxia , Wu Zhongtao
Published: February 2022

The functions of the materials composed of small molecules are highly dependent on their ordered molecular arrangements in both natural and artificial systems. Without ordered structure, small molecules hardly gain complicated functions, due to the absence of intermolecular covalent bond connection or strong network. Here, a low molecular weight spiropyran that could exhibit attractive photochromism and powerful adhesion property in disordered solid state is demonstrated. With maximum up to ∼8 MPa, the adhesion strength could be photoregulated in multiple levels, which also shows one‐to‐one correspondence to the specific color state. The working mechanism analysis on the photoregulated adhesion reveals that the isomer ratio of merocyanine form and the molecular packing density of spiropyran are the determining factors for the adhesion ability. The discovery of photoregulated adhesion from pure spiropyran provides a new strategy for developing functional materials by employing low molecular weight compounds.
Promoting GAINs (Give Attention to Limitations in Assays) over PAINs Alerts: no PAINS, more GAINs
Authors: Choo Malcolm Z. Y. , Chai Christina L. L.
Published: February 2022

Many concepts and guidelines in medicinal chemistry have been introduced to aid in successful drug discovery and development. An example is the concept of Pan‐Assay Interference Compounds (PAINS) and the elimination of such nuisance compounds from high‐throughput screening (HTS) libraries. PAINs, along with other guidelines in medicinal chemistry, are like double‐edged swords. If used appropriately, they may be beneficial for drug discovery and development. However, rigid and blind use of such concepts can hinder productivity. In this perspective, we introduce GAINS (give attention to limitations in assays) and highlight its relevance for successful drug discovery.
Study shows gaps in locating quality recovery housing
Authors: Knopf Alison
Published: February 2022

Many young people coming out of treatment for substance use disorders (SUDs) need a safe place — away from alcohol and other drugs — to live life. This is known as recovery housing, and one of the biggest problems for health care providers is finding out where it is and how good it is.
FDA warns about dental problems with buprenorphine medicines dissolved in the mouth
Authors: Knopf Alison
Published: February 2022

The U.S. Food and Drug Administration (FDA) is warning that dental problems have been reported with medicines containing buprenorphine that are dissolved in the mouth. The dental problems, including tooth decay, cavities, oral infections, and loss of teeth, can be serious and have been reported even in patients with no history of dental issues. Despite these risks, buprenorphine is an important treatment option for opioid use disorder (OUD) and pain, and the benefits of these medicines clearly outweigh the risks. Regular adherence to buprenorphine to treat OUD reduces withdrawal symptoms and the desire to use opioids, without causing the cycle of highs and lows associated with opioid misuse. The comprehensive approach of buprenorphine combined with counseling and other behavioral therapies is often one of the most effective ways to treat OUD. This approach, called medication‐assisted treatment (MAT), is tailored to meet each patient's needs and can help sustain recovery and prevent or reduce opioid overdose. According to the U.S. Substance Abuse and Mental Health Services Administration (SAMHSA), MAT has been shown to be effective in improving patient survival, decreasing opioid use, and allowing patients to live a self‐directed life, including the ability to gain and maintain employment.
Organocatalytic Diastereodivergent Enantioselective Formal oxa‐Diels‐Alder Reaction of Unsaturated Ketones with Enoates Under Liquid‐Assisted Grinding Conditions
Authors: Peňaška Tibor , Modrocká Viktória , Stankovianska Klára , Mečiarová Mária , Rakovský Erik , Šebesta Radovan
Published: February 2022

Chiral heterocycles occur in many compounds of interest, but their efficient synthesis is challenging. This study concerns the enantioselective and diastereoselective synthesis of densely substituted chiral pyran derivatives. Diastereodivergence of the oxa‐Diels‐Alder reaction is achieved by using either a bifunctional amino‐thiourea or a monofunctional quinine organocatalyst under ball‐milling conditions. Liquid‐assisted grinding proves a highly efficient means of affording pyrans in high yield, with high enantiomeric purities and short reaction times.
Effective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran by an Acetal Protection Strategy
Authors: Boonyakarn Tat , Wiesfeld Jan J. , Asakawa Miyuki , Chen Lulu , Fukuoka Atsushi , Hensen Emiel J. M. , Nakajima Kiyotaka
Published: February 2022

An acetal protection strategy for 5‐hydroxymethylfurfural (HMF) was used to obtain 2,5‐diformyfuran (DFF) using concentrated HMF solutions and a γ‐Al2O3‐supported Ru catalyst (Ru/γ‐Al2O3). The HMF‐acetal with 1,3‐propanediol can be oxidized to DFF‐acetal with a yield of 84.0 % at an HMF conversion of 94.2 % from a 50 wt % solution. In contrast, aerobic oxidation of nonprotected HMF using a 10 wt % solution afforded DFF only in a moderate yield (52.3 %). Kinetic studies indicated that the six‐membered ring acetal group not only prevents side reactions but also accelerates aerobic oxidation of the −CH2OH moiety to −CHO under retention of the acetal functionality. Organic deposits formed during the reaction explained the significant decrease in the activity of the Ru/γ‐Al2O3 catalyst, which could be recovered neither by washing in water or organic solvents, nor by a calcination‐reduction treatment. Sonication of the used Ru/γ‐Al2O3 catalyst in an aqueous NaOH solution successfully removed the deposits and allowed reuse of the catalyst for at least four times without activity loss.
Single miller capacitor frequency compensation techniques: Theoretical comparison and critical review
Authors: Grasso Alfio Dario , Marano Davide , Palumbo Gaetano , Pennisi Salvatore
Published: February 2022

This paper presents a systematic analytical comparison of the single‐Miller capacitor frequency compensation techniques suitable for three‐stage complementary metal–oxide–semiconductor (CMOS) operational transconductance amplifiers (OTAs). The comparison is carried out with the aid of a figure of merit that expresses a trade‐off among gain‐bandwidth product, load capacitance, and total transconductance, for equal values of the phase margin. The results found can be used before the transistor‐level design step and provide useful guidelines for the optimization of the small‐signal performance. Simulations by using a 65‐nm standard CMOS technology confirming the effectiveness of the theoretical comparison for 10 different OTA topologies are also provided.
A Bimetallic Ag/Ti‐Based Coordination Polymer as a Catalyst for Electrocatalytic CO2 Reduction and Selective Sulfide Oxidation
Authors: Wu Yi‐Xin , Ru Liu Xue , Yu Wei‐Dong , Li Lei‐Jiao , Pan Fuxing , Liu Weisheng , Liu Chao
Published: February 2022

The first example of heterometallic Ag/Ti bimetallic‐based coordination polymer was synthesized using salicylic acid as the ligand. The uniform Ag/Ti−O rod array has efficient electrocatalytic CO2 reduction activity with a Faradaic efficiency (FE) of 90.3 % at −0.88 V (vs RHE) and a maximum TOF of 658 h−1 at −1.08 V. The chemical catalytic property of the Ag/Ti−O rod was also studied, and the results showed that the Ag/Ti−O rod has good catalytic performance for selective oxidation of sulfide to sulfoxide.
A Modular Synthesis of Teraryl‐Based α‐Helix Mimetics, Part 4: Core Fragments with Two Halide Leaving Groups Featuring Side Chains of Proteinogenic Amino Acids
Authors: Trobe Melanie , Blesl Julia , Vareka Martin , Schreiner Till , Breinbauer Rolf
Published: February 2022

Teraryl‐based α‐helix mimetics have proven to be useful compounds for the inhibition of protein‐protein interactions (PPI). We have developed a modular and flexible approach for the synthesis of teraryl‐based α‐helix mimetics using a benzene core unit featuring two halide leaving groups of differentiated reactivity in the Pd‐catalyzed cross‐coupling used for teraryl assembly. The use of para‐bromo iodoarene core fragments resolved the issue of hydrolysis during cross‐coupling that was observed when using triflate as a leaving group. We report a complete set of para‐bromoiodoarene core fragments decorated with side chains of all proteinogenic amino acids relevant for PPI (Ala, Arg, Asn, Asp, Cys, Gln, Glu, His, Ile, Leu, Lys, Met, Phe, Ser, Thr, Trp, Tyr and Val). In order to be compatible with general cross‐coupling conditions, some of the nucleophilic side chains had to be provided in a protected form to serve as stable building blocks.
A Modular Synthesis of Teraryl‐Based α‐Helix Mimetics, Part 5: A Complete Set of Pyridine Boronic Acid Pinacol Esters Featuring Side Chains of Proteinogenic Amino Acids
Authors: Trobe Melanie , Schreiner Till , Vareka Martin , Grimm Sebastian , Wölfl Bernhard , Breinbauer Rolf
Published: February 2022

Teraryl‐based α‐helix mimetics have proven to be useful compounds for the inhibition of protein‐protein interactions (PPI). We have developed a modular and flexible approach for the synthesis of teraryl‐based α‐helix mimetics using pyridine containing boronic acid building blocks to increase the water solubility. Following our initial publication in which we have introduced the methodology in combination with sequential Pd‐catalyzed cross‐coupling for teraryl assembly, we can now report a complete set of pyridine based boronic acid building blocks decorated with side chains of all proteinogenic amino acids relevant for PPI (Ala, Arg, Asn, Asp, Cys, Gln, Glu, His, Ile, Leu, Lys, Met, Phe, Ser, Thr, Trp, Tyr, Val) to complement the core fragment set. For a representative set of teraryls we have studied the influence of the pyridine rings on the solubility of the assembled oligoarenes.
Efficient Synthesis of Bis(5‐arylfuran‐2‐yl)methane Scaffolds Utilizing Biomass‐Derived Starting Materials
Authors: Chacón‐Huete Franklin , Covone Jason , Zaroubi Liana , Forgione Pat
Published: February 2022

A new synthetic route utilizing biomass‐derived furans as a starting material for the production of bis(5‐arylfuran‐2‐yl)methane scaffolds was developed. Decarboxylative cross‐coupling of 5‐hydroxymethylfuroic acid (HMFA) was studied in detail with overall good yields. Acid‐catalyzed self‐condensation was optimized to produce the target structures in excellent yields. Overall, this report introduces a new expedient synthesis to obtain bis(furyl) methane scaffolds that avoids the use of protecting groups and highlights the utilization of renewable carbon sources as starting materials.
KOtBu/DMSO Catalytic System for Isomerization of Allylic Alcohols to Ketones
Authors: Sai Masahiro
Published: February 2022

The isomerization of allylic alcohols is an important reaction because it can afford carbonyl compounds in an atom‐economical manner. Although base‐catalyzed methods are more desirable than those using transition‐metal catalysts from both the economic and environmental points of view, these methods have several drawbacks, such as narrow substrate scope and high catalyst loading. This paper reports the development of an efficient KOtBu/DMSO catalytic system suitable for the isomerization of a broad range of allylic alcohols with good yields, to which previously reported systems could not be applied. This catalytic system was successfully applied to a tandem allylic isomerization/electrophilic trapping reaction, thereby highlighting its synthetic utility.
Direct Protein Detection in Solutions of High Ionic Strength using Polyethylene Glycol‐modified AlGaN/GaN High Electron Mobility Transistors
Authors: Diao Lina , Xu Zhan , Zhang Wangyang , Miao Bin , Hu Yimin , Gu Zhiqi , Li Jiadong
Published: February 2022

Herein, we proposed a simple 3‐(aminopropyl) triethoxysilane/polyethylene glycol (APTES/PEG)‐AlGaN/GaN high electron mobility transistors (HEMT) biosensor that enabled direct detection in high ionic strength solutions. Unlike previous modification strategies, the PEG‐modified on the GaN surface established a stable screening system by forming a porous biopolymer layer, which can overcome Debye shielding. In our work, the APTES/PEG modification enabled immunoglobulin G (IgG) to be easily detected in solutions with concentrations of up to 30 mM (3x) of phosphate buffered saline (PBS), indicating that the APTES/PEG modification strategy had the potential for direct detection of biomolecules in physiological solutions, which provided a new method for bio‐surface modification on GaN and advanced the practical application of AlGaN/GaN HEMT biosensors.
Formulation and production of persimmon milk drink and evaluation of its physicochemical, rheological, and sensorial properties
Authors: Jokar Akbar , Azizi Mohamad Hossyn
Published: February 2022

One of the effective ways for increasing milk intake in a diet is producing flavored milk. In the present study, flavored persimmon milk drinks were formulated and produced. Rheological, sensorial, and physicochemical properties of the drinks were evaluated. Different amounts of persimmon (5, 10, 20, and 30% W/V), gum Arabic (0.1 and 0.2% W/V), and sugar (3 and 5% W/V) were used to produce persimmon milk. All the experiments were done in a completely randomized design (CRD) in three replicates. First, persimmons were mixed thoroughly in a blender then, according to the formulation, whole milk was added to it and mixed again. The obtained mixture was heated up to 50 ᵒC then sugar and the gum were added and mixed completely for 3 min. The drink was pasteurized at 90 ᵒC for 1 min. Sensorial analysis revealed that the most acceptable persimmon milk was related to 0.1% gum Arabic, 5% sugar, and 10% persimmon. Flow behavior of the drinks with 20 and 30% persimmon was Non‐Newtonian, while 10% persimmon samples with and without gum showed Newtonian behavior. The drinks with 20 and 30% persimmon were pseudoplastic, and their apparent viscosity increased by increasing shear rates. By applying a proper content of persimmon in milk, we can produce a nutritious flavored milk drink with acceptable taste, stability, and consistency. As this drink has high nutrient contents like phenol, dietary fiber, vitamins, antioxidants, etc., it can help promote health, especially for children.
Tapping into emerging markets: EMNEs' strategies for innovation capability building
Authors: Lopez‐Vega Henry , Lakemond Nicolette
Published: February 2022

Research Summary

This article explores EMNEs' innovation capability building in emerging markets. The paper provides a longitudinal account of how the Brazilian cosmetics firm Natura transitioned from scant to ample innovation resources and processes. Building on the institution‐based view and the resource‐based view, we explain how EMNEs' innovation capability building is anchored in open innovation and collaborative nonmarket strategies. The paper reveals a unique pattern of innovation capability building based on a combination of local and global open innovation processes and harnessing the country characteristics over time. It is shown how combining open innovation and collaborative nonmarket strategies can help mitigate weak formal and informal institutions in emerging markets. The study offers an integrated framework explaining innovation capability building and the effects on the institutional setting.

Managerial Summary

The increase of well‐known EMNEs has raised interest in understanding how these firms build sustainable innovation capabilities. Based on a longitudinal study of the Brazilian‐based cosmetics firm Natura, this paper shows how an open innovation strategy can be used to tap into home‐market natural resources and connect to the global setting. This innovation capability process involves traditional market‐based strategies like inter‐organizational collaborations but also nonmarket strategies, such as developing local relationships, supporting socio‐biodiversity, and contributing to local society. The findings point at the importance of developing an overall innovation strategy, directing attention to innovation processes, engaging in recursive practice in innovation projects, responding to the market and nonmarket environments, and linking the emerging market institutional setting and the global market context.
Youth experiences of racism and family ethnic‐racial socialization in Germany: What we (don't) know
Authors: Juang Linda P. , Schwarzenthal Miriam , Aral Tuğçe , Pevec Sharleen
Published: February 2022

In 1988 the youth‐led movement “Schools without racism, schools with courage” was established in Belgium and quickly spread throughout Europe. German schools adopted this movement in 1995. Decades later, racism is not yet a strong developmental science research topic for studies of youth in Germany and Europe. In this commentary we argue that it should be. With increasing hate crimes and harassment, there is also a need to understand how families are socializing young people to be prepared for, cope with, resist, and disrupt racism. This type of ethnic‐racial socialization affects important developmental processes—adolescent ethnic‐racial identity development and intergroup and institutional understanding and relations—and requires a more prominent place of study in a migration‐diverse Germany. Studying these issues in this particular sociohistorical context will also contribute to a more context‐specific understanding of youth experiences of racism.
Navigating the impact of the community on community college diversity, equity, and inclusion
Authors: Hubbard‐Jackson Chris
Published: February 2022

American community colleges are typically public 2‐year higher education institutions with a history and mission of providing educational access to the people in the communities in which they are located and serve. Nationally community colleges continue to become more diverse, providing increased access especially for the socioeconomically disadvantaged, women, and other marginalized groups (Malcom, 2012). Since community colleges continue to become more diverse, many have focused their attention on diversity, equity, and inclusion (D.E.I.) efforts. These efforts are impacted by the local community (location and culture). In this article, the researcher used geography of college choice and Braddock's perpetuation hypothesis as the frameworks for examining the impact of the community on community college campus diversity, as well as D.E.I. efforts. The researcher also provides recommendations including how to use data to navigate the impact of the community on the community college's diversity and D.E.I. efforts.
Vegetation of natural and stabilized riverbanks and early effects of removal of bank fixation
Authors: Seele‐Dilbat Carolin , Kretz Lena , Wirth Christian
Published: February 2022

The majority of rivers in Europe has been dramatically altered in terms of their morphology and hydrology with severe consequences for the diversity and ecological functioning of the rivers and their floodplains. Consequently, an increasing number of river reaches has been restored over the past decades, often including the removal of bank fixation to reinitiate bank erosion and allowing for a rewidening of the rivers' cross‐section. However, monitoring in detail the effect of such a measure on riverine vegetation is scarce. Using a Before‐After‐Control‐Impact (BACI) design, we analysed the early changes of the vegetation 2 years after the removal of bank fixation at the Mulde River (central Germany). The results were compared with two types of control sites, representing a nonrestored as well as a natural riverbank that has never been fixed. We analysed differences in taxonomic and functional composition of the vegetation between bank types as well as community turnover after restoration. Two years after restoration, the vegetation differed clearly from the nonrestored sites. A substantial proportion of the community, especially the newly established species, became more similar to the natural bank community. Most importantly, spatiotemporal heterogeneity of the vegetation increased after removal of bank fixation, being an indicator for re‐established dynamic processes similar to the natural site. The presented data serve as a baseline for a long‐term monitoring and quantitative meta‐analysis of restoration effects.
Serum/glucocorticoid‐regulated kinase 1‐targeted transient receptor potential oxalate subtype 1 regulates bladder smooth muscle cell proliferation due to bladder outlet obstruction in mice via activated T cell nuclear factor transcription factor 2
Authors: He Jiangshu , Yang Jin , Chen Lin , He Pinglin , Liu Xun , Wang Kai , Dong Taotao , Li Jia , Ma Xudong , Bastian Amend , Arnulf Stenzl
Published: February 2022

Bladder outlet obstruction (BOO) is a type of chronic disease that is mainly caused by benign prostatic hyperplasia. Previous studies discovered the involvements of both serum/glucocorticoid‐regulated kinase 1 (SGK1) and activated T cell nuclear factor transcription factor 2 (NFAT2) in the proliferation of smooth muscle cells after BOO. However, the relationship between these two molecules is yet to be explored. Thus, this study explored the specific mechanism of the SGK1‐NFAT2 signaling pathway in mouse BOO‐mediated bladder smooth muscle cell proliferation in vivo and in vitro. In vivo experiments were performed by suturing 1/2 of the external urethra of female BALB/C mice to cause BOO for 2 weeks. In vitro, mouse bladder smooth muscle cells (MBSMCs) were treated with dexamethasone (Dex) or dexamethasone + SB705498 for 12 h and were transfected with SGK1 siRNA for 48 h. The expression and distribution of SGK1, transient receptor potential oxalate subtype 1 (TRPV1), NFAT2, and proliferating cell nuclear antigen (PCNA) were measured by Western blotting, polymerase chain reaction, and immunohistochemistry. The relationship between SGK1 and TRPV1 was analyzed by coimmunoprecipitation. The proliferation of MBSMCs was examined by 5‐ethynyl‐2′‐deoxyuridine and cell counting kit 8 assays. Bladder weight, smooth muscle thickness, and collagen deposition in mice after 2 weeks of BOO were examined. Bladder weight, smooth muscle thickness, the collagen deposition ratio, and the expression of SGK1, TRPV1, NFAT2, and PCNA were significantly increased in mice after 2 weeks of BOO. Compared with the control, 10 μM Dex promoted the expression of these four molecules and the proliferation of MBSMCs. After inhibiting TRPV1, only the expression of SGK1 was not affected, and the proliferation of MBSMCs was inhibited. After silencing SGK1, the expression of these four molecules and the proliferation of MBSMCs decreased. Coimmunoprecipitation suggested that SGK1 acted directly on TRPV1. In this study, SGK1 targeted TRPV1 to regulate the proliferation of MBSMCs mediated by BOO in mice through NFAT2 and then affected the process of bladder remodeling after BOO. This finding may provide a strategy for BOO drug target screening.